asymmetric allylboration reactions with …

S1

ASYMMETRIC ALLYLBORATION REACTIONS WITH SODERQUIST’S CHIRAL 10-

SUBSTITUTED-9-BORABICYCLO[3.3.2]DECANES: A THEORETICAL STUDY

Ariel M. Sarotti and Silvina C. Pellegrinet*

Instituto de Química Rosario (CONICET), Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de

Rosario, Suipacha 531, Rosario (2000), Argentina

Supporting Information

List of contents:

- Computational methods. Page S2.

- Optimized geometries of all structures included in this study with key distances (in Å). Energies including zero-point

energy (ZPE) corrections, enthalpies, free energies and free energies in solution of transition structures and intermediates

relative to reactants for the allylboration reactions of acetaldehyde (3) and acetophenone (4) using (-)-B-Allyl-10-TMS-9-

BBD (1) and (-)-B-allyl-10-Ph-9-BBD (2) (Figures S1- S13 and Tables S1- S8). Pages S3- S11.

- Cartesian coordinates, absolute energies including ZPE (in hartrees), free energies and free energies in solution of all the

stationary points included in this study; number of imaginary frequencies and values of imaginary frequencies of all

transition structures. Energies of the frontier molecular orbitals of the reactants (in eV). Pages S12-S47.

3 4

H3C Ph

OB

Ph

2

H CH3

OB

TMS

1

S2

Computational methods

All DFT calculations were performed using Gaussian 03.1 Density functional theory (DFT) calculations were carried out

with the B3LYP2 functional and the 6-31G* basis set.3 The choice of this level of theory for the present investigation was

based on our previous experience on the study of reactions of organoboranes,4 including the study of the catalytic asymmetric

allylboration of ketones,4g and also on a theoretical study on allylboration reactions using tartrate ester-derived allylboronates

by Roush and co-workers.5 Geometries for all structures were fully optimized and normal coordinate analyses were used to

confirm the nature of the stationary points. All transition structures were confirmed to have only one imaginary frequency

corresponding to the formation of the expected bonds. Intrinsic Reaction Coordinate (IRC) calculations were performed to

determine the connections between stationary points. Wiberg Bond Indices were calculated using the Natural Bond Orbital

(NBO) program as implemented in Gaussian 03.6 Reported thermochemical properties include zero-point energies (ZPEs)

without scaling and were calculated at 1 atm and 298.15 K. Free energies in solution were computed on the structures

optimized in the gas phase at the B3LYP/6-31G* level of theory with the Polarizable Continuum Model (PCM) as

implemented in Gaussian 03 using diethyl ether or THF as the solvent for the reactions of 1 and 2, respectively.7 Selectivity

ratios were calculated from the Boltzmann factors of the four most stable TSs and corresponding complexes using Gibbs free

energies in solution.

Conformational searches were performed to locate the minimum energy conformers of all the structures. Initially, a large

number of geometries were generated using the conformational search module of Hyperchem8 with the MM+ method.9

Selected structures were then successively reoptimized at the RHF/AM1, RHF/3-21G and B3LYP/6-31G* levels of theory.

For the products, the global minima located after following this procedure were more stable than the conformers found by

IRC calculations. The computational data of such conformers is given below. For transition structures, the atoms of the six-

membered chairlike substructure were fixed during initial Hyperchem conformational searches.

1. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A., Jr., Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y. Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Gonzalez, C.; Pople, J. A. Gaussian 03, Revision C.02, Gaussian, Inc., Wallingford CT, 2004.

2. (a) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785-789. (b) Becke, A. D. J. Chem. Phys. 1993, 98, 1372-1377. (c) Becke, A. D. J. Chem.

Phys. 1993, 98, 5648-5652. 3. (a) Hehre, W. J.; Ditchfield, R.; Pople, J. A. J. Chem. Phys. 1972, 56, 2257-2261. (b) Hariharan, P. C.; Pople, J. A. Teor. Chim. Acta 1973, 28, 213-222. 4. For example see: (a) Pellegrinet, S. C.; Silva, M. A.; Goodman, J. M. J. Am. Chem. Soc. 2001, 123, 8832-8837. (b) Silva, M. A.; Pellegrinet, S. C.;

Goodman, J. M. J. Org. Chem. 2002, 67, 8203-8209. (c) Silva, M. A.; Pellegrinet, S. C.; Goodman, J. M. J. Org. Chem. 2003, 68, 4059-4066. (d) Silva, M. A.; Pellegrinet, S. C.; Goodman, J. M. Arkivoc 2003, X, 556-565. (e) Pellegrinet, S. C.; Goodman, J. M. J. Am. Chem. Soc. 2006, 128, 3116-3117; (f) Paton, R. S.; Goodman, J. M.; Pellegrinet S. C. J. Org. Chem. 2008, 73, 5078-5089. (g) Paton, R. S.; Goodman, J. M.; Pellegrinet, S. C. Org. Lett., 2009, 11, 37-40.

5. Gung, B. W.; Xue, X.; Roush, W. R. J. Am. Chem. Soc. 2002, 124, 10692-10697. 6. NBO Version 3.1, Glendening, E. D.; Reed, A. E.; Carpenter, J. E.; Weinhold, F. For some original literature references, see: (a) Reed, A. E.;

Weinstock, R. B.; Weinhold, F. J. Chem. Phys. 1985, 83, 735-746. (b) Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899-926. 7. For a review on continuum solvation models, see: Tomasi, J.; Mennucci, B.; Cammi, R. Chem. Rev. 2005, 105, 2999-3093. 8. Hyperchem Professional Release 7.52, Hypercube, Inc., 2005. 9. Allinger, N. L. J. Am. Chem. Soc. 1977, 99, 8127-8134 (MM2).

S3

Figure S1. Optimized geometries for reagents 1-4.

(-)-B-Allyl-10-TMS-9-BBD (1) (-)-B-Allyl-10-Ph-9-BBD (2)

acetaldehyde (3) acetophenone (4)

S4

Figure S2. Optimized geometries for the transition structures found for the allylboration reaction between 1 and 3.

TS-1+3-ReSyn-BC TS-1+3-SiAnti-BCTS-1+3-SiAnti-CB

1.57

2.41

1.57

2.36

1.57

2.35

B

C1C2

C3

C1Ó

B

C1C2

C3

C1´ O

B

C1C2

C3

C1Ó

2.16

TS-1+3-ReSyn-CB

1.58

2.40

B

C1 C2

C3

C1Ó

B

C1

C2C3

C1´

O1.56

2.37

B

C1

C2

C3

C1´

O1.56

2.34

B

C1

C2

C3

C1´

O1.57

2.41

B

C1

C2

C3

C1´

O1.57

2.41

TS-1+3-ReAnti-BC TS-1+3-SiSyn-BCTS-1+3-SiSyn-CBTS-1+3-ReAnti-CB

Table S1. Energies including zero-point energy (ZPE) corrections, enthalpies, free energies and free energies in solution of transition structures relative to reactants for the reaction of 1 with 3.

TS ∆E‡0

(kcal mol-1) ∆H‡

(kcal mol-1) ∆G‡


sol (kcal mol-1)

TS-1+3-ReSyn-CB 2.07 0.64 16.87 -1.65

TS-1+3-ReSyn-BC 2.02 0.72 16.53 -1.15

TS-1+3-SiAnti-CB 5.45 4.17 19.81 2.59

TS-1+3-SiAnti-BC 5.13 3.82 19.50 2.36

TS-1+3-ReAnti-CB 8.87 7.27 24.19 5.17

TS-1+3-ReAnti-BC 8.90 7.38 23.61 5.57

TS-1+3-SiSyn-CB 9.47 7.99 24.46 5.77

TS-1+3-SiSyn-BC 10.12 8.77 24.67 6.98

S5

Figure S3. Optimized geometries for the complexes found for the allylboration reaction between 1 and 3.

(1-3)-ReSyn-CB (1-3)-ReSyn-BC (1-3)-SiAnti-CB (1-3)-SiAnti-BC

B

C1

C2

C3

C1´

O

B

C1C2

C3

C1´

O

B

C1C2

C3

C1´

O

B

C1C2

C3

C1´

O

1.68 1.65 1.68 1.68

Figure S4. Optimized geometries for the products found for the allylboration reaction between 1 and 3.

P-1+3-S(Global minimum)

P-1+3-R(Global minimum)

P-1+3-S(from IRC of TS-1+3-ReSyn-CB)

P-1+3-R(from IRC of TS-1+3-SiAnti-BC)

Table S2. Energies including zero-point energy (ZPE) corrections, enthalpies, free energies and free energies in solution of complexes and products relative to reactants for the reaction of 1 with 3.

Structure ∆E‡0




sol (kcal mol-1)

(1-3)-ReSyn-CB 0.95 0.40 14.41 -1.84

(1-3)-ReSyn-BC 1.49 0.89 14.85 -1.39

(1-3)-SiAnti-CB 4.10 3.67 17.18 2.04

(1-3)-SiAnti-BC 3.67 3.20 16.89 1.71

P-1+3-S (Global minimum) -40.95 -41.59 -29.15 -42.37

P-1+3-S (from IRC of TS-1+3-ReSyn-CB) -39.82 -40.52 -27.81 -41.81

P-1+3-R (Global minimum) -40.57 -41.13 -29.07 -42.77

P-1+3-R (from IRC of TS-1+3-SiAnti-BC) -40.24 -40.93 -27.97 -42.49

S6


TS-2+3-ReSyn-CB TS-2+3-ReSyn-BC TS-2+3-SiAnti-CB TS-2+3-SiAnti-BC

1.55

2.40

B

C1C2

C3

C1Ó

1.54

2.44

B

C1C2

C3

C1Ó

1.57

2.36

B

C1C2

C3

C1´ O1.57

2.40

B

C1C2

C3

C1Ó

TS-2+3-ReAnti-CB TS-2+3-ReAnti-BC TS-2+3-SiSyn-CB TS-2+3-SiSyn-BC

B

C1

C2C3

C1´

O1.57

2.37

B

C1

C2C3

C1´

O

1.58

2.40

B

C1

C2

C3

C1´

O

1.56

2.40

B

C1

C2

C3

C1´

O

1.56

2.39


TS ∆E‡0




sol (kcal mol-1)

TS-2+3-ReSyn-CB 0.51 -0.97 15.60 -3.10

TS-2+3-ReSyn-BC 0.76 -0.66 15.62 -2.76

TS-2+3-SiAnti-CB 2.02 0.53 17.04 -2.17

TS-2+3-SiAnti-BC 1.64 0.21 16.52 -2.12

TS-2+3-ReAnti-CB 1.87 0.39 17.20 -1.31

TS-2+3-ReAnti-BC 1.47 -0.03 16.63 -1.77

TS-2+3-SiSyn-CB 1.99 0.51 17.25 -1.09

TS-2+3-SiSyn-BC 2.57 1.10 17.63 -0.50

S7


(2-3)-SiAnti-CB (2-3)-SiAnti-BC(2-3)-ReSyn-CB (2-3)-ReSyn-BC

1.61B

C1C2

C3

C1´O1.60

B

C1C2

C3

C1´O1.68

B

C1C2

C3

C1´ O1.68

B

C1C2

C3

C1´ O




P-2+3-S(from IRC of TS-2+3-ReSyn-CB)

P-2+3-R(from IRC of TS-2+3-SiAnti-CB)


Structure ∆E‡0




sol (kcal mol-1)

(2-3)-ReSyn-CB -0.09 -0.89 14.08 -3.35

(2-3)-ReSyn-BC 0.38 -0.37 14.20 -2.82

(2-3)-SiAnti-CB 0.64 0.09 13.99 -2.66

(2-3)-SiAnti-BC 0.43 -0.06 13.88 -2.65


P-2+3-S (from IRC of TS-2+3-ReSyn-CB) -38.80 -39.58 -26.72 -40.42


P-2+3-R (from IRC of TS-2+3-SiAnti-CB) -38.79 -39.56 -26.93 -41.00

S8


2.23

B

C1 C2

C3

C1´O

C10

2.23

B

C1C2

C3

C1´O

C10

2.21

B

C1C2

C3

C1´

O

C10

2.20

B

C1C2

C3

C1´

OC10

B

C1

C2

C3

C1´

O1.52

2.21

BC1

C2

C3

C1´

O

1.52

2.21

B

C1

C2

C3

C1´

O1.55

2.19

B

C1

C2

C3

C1´

O1.55

2.24

TS-1+4-ReSyn-BC TS-1+4-SiAnti-BCTS-1+4-SiAnti-CBTS-1+4-ReSyn-CB



TS ∆E‡0




sol (kcal mol-1)

TS-1+4-ReSyn-CB 15.13 13.97 31.19 12.26

TS-1+4-ReSyn-BC 15.27 14.17 31.20 12.62

TS-1+4-SiAnti-CB 15.58 14.53 31.41 13.26

TS-1+4-SiAnti-BC 15.39 14.42 30.85 13.62

TS-1+4-ReAnti-CB 19.64 18.41 35.93 16.89

TS-1+4-ReAnti-BC 19.28 18.07 35.57 16.86

TS-1+4-SiSyn-CB 23.43 22.45 39.29 21.27

TS-1+4-SiSyn-BC 24.19 23.33 38.89 21.93

S9



B

C1C2

C3 C1´O

3.70 B

C1C2C3

C1´ O3.62

B

C1

C2

C3

C1´O

4.39

B

C1C2

C3

C1´

O3.82




P-1+4-R(from IRC of TS-1+4-ReSyn-CB)

P-1+4-S(from IRC of TS-1+4-SiAnti-CB)


Structure ∆E‡0




sol (kcal mol-1)

(1-4)-ReSyn-CB -0.65 0.16 8.69 1.90

(1-4)-ReSyn-BC -2.17 -1.27 5.21 1.69

(1-4)-SiAnti-CB -0.41 0.54 7.41 3.57

(1-4)-SiAnti-BC -1.99 -1.21 7.34 3.40


P-1+4-R (from IRC of TS-1+4-ReSyn-CB) -20.61 -21.05 -6.88 -21.73


P-1+4-S (from IRC of TS-1+4-SiAnti-CB) -21.17 -21.66 -6.78 -23.55

S10


1.51

2.20

B

C1 C2

C3

C1Ó

1.51

2.20

B

C1

C2

C3

C1Ó1.52

2.18

B

C1C2

C3

C1Ó

1.53

2.18

B

C1C2

C3

C1´

O

B

C1

C2

C3

C1´

O1.52

2.17

B

C1

C2C3

C1´

O1.52

2.19

B

C1

C2 C3C1´

O1.52

2.17

B

C1

C2C3 C1´

O1.52

2.20

TS-2+4-ReSyn-BC TS-2+4-SiAnti-BCTS-2+4-SiAnti-CBTS-2+4-ReSyn-CB



TS ∆E‡0




sol (kcal mol-1)

TS-2+4-ReSyn-CB 9.49 8.30 25.92 7.33

TS-2+4-ReSyn-BC 10.67 9.55 26.80 9.16

TS-2+4-SiAnti-CB 12.17 11.09 28.29 10.20

TS-2+4-SiAnti-BC 11.81 10.67 27.81 10.13

TS-2+4-ReAnti-CB 12.21 11.06 28.56 10.30

TS-2+4-ReAnti-BC 11.02 9.82 27.35 9.15

TS-2+4-SiSyn-CB 14.13 13.02 30.29 11.77

TS-2+4-SiSyn-BC 15.10 13.98 31.08 12.78

S11



B

C1C2

C3

C1´O

1.68B

C1C2

C3

C1´

O1.68 B

C1 C2

C3

C1´

O

3.66

B

C1C2C3

C1´O

3.26




P-2+4-R(from IRC of TS-2+4-ReSyn-CB)

P-2+4-S(from IRC of TS-2+4-SiAnti-BC)


Structure ∆E‡0




sol (kcal mol-1)

(2-4)-ReSyn-CB 3.17 2.92 18.12 1.89

(2-4)-ReSyn-BC 4.42 4.21 19.19 3.16

(2-4)-SiAnti-CB -2.37 -1.51 7.31 1.48

(2-4)-SiAnti-BC -2.00 -1.06 6.74 4.01


P-2+4-R (from IRC of TS-2+4-ReSyn-CB) -22.88 -23.32 -8.52 -24.00


P-2+4-S (from IRC of TS-2+4-SiAnti-BC) -23.60 -23.95 -9.71 -23.96

S12

Reactants

B-Allyl-10-TMS-9-BBD (1)

B3LYP/6-31G* Geometry C 0 0.033646 -2.037628 -1.511490 C 0 -0.192429 -1.580200 -0.028717 C 0 0.948700 -1.136398 -2.368134 C 0 2.391968 -0.868835 -1.894913 B 0 0.000000 0.000000 0.000000 C 0 0.649033 -2.401932 0.986023 C 0 1.427124 0.653030 -0.028915 C 0 2.602478 -0.273010 -0.466782 C 0 2.128235 -2.617554 0.647736 C 0 -1.303452 0.932129 -0.028549 Si 0 1.790543 1.710617 1.551895 C 0 2.998337 -1.359207 0.564423 C 0 -2.360245 0.487076 -1.005249 C 0 3.641647 2.124329 1.631439 C 0 1.273056 0.870255 3.175491 C 0 0.861542 3.363113 1.453033 C 0 -2.747086 1.168533 -2.086838 H 0 0.403473 -3.072113 -1.527496 H 0 -0.939194 -2.059494 -2.017014 H 0 -1.239075 -1.814896 0.211807 H 0 1.006317 -1.570100 -3.376144 H 0 0.440598 -0.170761 -2.506226 H 0 2.829147 -0.173279 -2.624313 H 0 2.982803 -1.791138 -1.983719 H 0 0.186615 -3.395874 1.079239 H 0 0.568954 -1.946426 1.983994 H 0 1.355743 1.473129 -0.768097 H 0 3.494186 0.363495 -0.546539 H 0 2.206375 -3.172531 -0.295731 H 0 2.561661 -3.280900 1.409409 H 0 -1.727875 0.882584 0.992600 H 0 -1.060135 1.985260 -0.211243 H 0 3.063538 -0.904770 1.561783 H 0 4.020981 -1.682831 0.322021 H 0 -2.821716 -0.481506 -0.809433 H 0 3.971115 2.656158 0.730438 H 0 4.273163 1.236649 1.742752 H 0 3.838943 2.779984 2.489029 H 0 1.814316 -0.063217 3.364487 H 0 0.200623 0.638824 3.187683 H 0 1.468536 1.539734 4.022903 H 0 -0.223145 3.243759 1.543381 H 0 1.062164 3.888748 0.511551 H 0 1.187347 4.019440 2.270081 H 0 -3.502670 0.782211 -2.765747 H 0 -2.326340 2.142273 -2.331146 B3LYP/6-31G* Energy = -903.014925 B3LYP/6-31G* Free Energy = -903.062372 B3LYP/6-31G* Free energy in solution = -903.412343 Number of Imaginary Frequencies = 0 HOMO = -6.35 LUMO = -0.15

B-Allyl-10-Ph-9-BBD (2) B3LYP/6-31G* Geometry C 0 -0.464203 -2.209961 -1.345642

C 0 -0.731094 -1.410172 -0.030746 C 0 0.815674 -1.848770 -2.122100 C 0 2.176041 -1.988968 -1.410477 B 0 0.000000 0.000000 0.000000 C 0 -0.392914 -2.234726 1.250519 C 0 1.587845 0.125259 -0.030685 C 0 2.394241 -1.210693 -0.078186 C 0 0.956055 -2.965927 1.265976 C 0 -0.872925 1.333206 -0.030487 C 0 2.218292 -2.097733 1.177353 C 0 -1.520416 1.407440 -1.393188 C 0 2.154022 1.097610 0.999603 C 0 -1.138900 2.215347 -2.387314 C 0 3.205643 1.961136 0.652893 C 0 1.675186 1.156082 2.318207 C 0 3.760361 2.842072 1.581055 C 0 2.225540 2.035110 3.253189 C 0 3.272278 2.881882 2.888611 H 0 -0.481125 -3.287918 -1.133545 H 0 -1.304321 -2.032913 -2.029100 H 0 -1.816116 -1.238937 0.018982 H 0 0.851669 -2.471542 -3.026886 H 0 0.711426 -0.818420 -2.490555 H 0 2.936020 -1.653687 -2.129303 H 0 2.388702 -3.052795 -1.237350 H 0 -1.181854 -2.989853 1.379730 H 0 -0.463745 -1.588120 2.139420 H 0 1.754166 0.615982 -1.008423 H 0 3.454758 -0.921875 -0.068253 H 0 0.969925 -3.707855 0.457230 H 0 1.012039 -3.551178 2.194458 H 0 -1.659683 1.281311 0.738403 H 0 -0.280121 2.234924 0.156876 H 0 2.291900 -1.464844 2.071274 H 0 3.083054 -2.774719 1.224762 H 0 -2.338409 0.708800 -1.574371 H 0 -1.631531 2.199997 -3.355865 H 0 -0.330856 2.933502 -2.262772 H 0 3.593369 1.940796 -0.363754 H 0 0.854309 0.509521 2.621155 H 0 4.571823 3.500702 1.281525 H 0 1.831726 2.058914 4.266174 H 0 3.700760 3.568466 3.613876 B3LYP/6-31G* Energy = -725.411896 B3LYP/6-31G* Free Energy = -725.457690 B3LYP/6-31G* Free energy in solution = -725.79459 Number of Imaginary Frequencies = 0 HOMO = -6.35 LUMO = -0.59 Acetaldehyde (3)

B3LYP/6-31G* Geometry C 0 -0.049927 -1.507431 0.000000 C 0 0.000000 0.000000 0.000000 O 0 -0.971817 0.721817 -0.000015 H 0 -1.085159 -1.855988 -0.000031 H 0 0.477493 -1.897217 -0.880737 H 0 0.477417 -1.897202 0.880722 H 0 1.026245 0.433640 -0.000015 B3LYP/6-31G* Energy = -153.774296

S13

B3LYP/6-31G* Free Energy = -153.799250 B3LYP/6-31G* Free energy in solution = -153.828752 (1) B3LYP/6-31G* Free energy in solution = -153.829124 (2) Number of Imaginary Frequencies = 0 HOMO = -6.94 LUMO = -0.59 (1) Diethyl ether (2) THF Acetophenone (4)

B3LYP/6-31G* Geometry C 0 3.697296 0.791077 0.000092 C 0 3.703339 2.189500 0.000488 C 0 2.489456 0.100891 -0.000061 C 0 1.270447 0.797440 0.000168 C 0 1.286224 2.200363 0.000565 C 0 2.497284 2.892471 0.000748 C 0 0.000000 0.000000 0.000000 C 0 -1.330368 0.736374 -0.000031 O 0 0.031189 -1.221375 -0.000107 H 0 4.635681 0.243149 -0.000092 H 0 4.646500 2.729600 0.000626 H 0 2.459137 -0.983810 -0.000366 H 0 0.355270 2.759140 0.000763 H 0 2.499405 3.979065 0.001068 H 0 -2.136002 0.000381 -0.000427 H 0 -1.426254 1.378632 0.883530 H 0 -1.425919 1.379257 -0.883224 B3LYP/6-31G* Energy = -384.757500 B3LYP/6-31G* Free Energy = -384.790125 B3LYP/6-31G* Free energy in solution = -384.894316 (1) B3LYP/6-31G* Free energy in solution = -384.895126 (2) Number of Imaginary Frequencies = 0 HOMO = -6.72 LUMO = -1.47 (1) Diethyl ether (2) THF Allylboration Reaction between 1 and 3 Complex (1-3)-ReSyn-CB

B3LYP/6-31G* Geometry O 0 -1.233032 -0.143417 0.000015 C 0 0.000000 0.000000 0.000000 C 0 0.624557 1.346069 -0.160950 B 0 -2.043930 -1.553329 0.399857 C 0 -1.221817 -2.784943 -0.290863 C 0 -3.611816 -1.338013 -0.017151 C 0 -1.853531 -1.469467 2.064804 C 0 -1.769165 -4.176758 0.131607 C 0 -1.044540 -2.682220 -1.836273 C 0 -4.202225 -2.352737 -1.053100 Si 0 -4.259323 0.446000 -0.282822 C 0 -0.445114 -1.441193 2.525253 C 0 -3.015000 -4.677429 -0.608032 C 0 -4.270737 -3.805206 -0.504288 C 0 -2.105667 -1.877182 -2.606537 C 0 -3.582291 -2.290894 -2.479019 C 0 -6.156342 0.388580 -0.454346 C 0 -3.897736 1.532776 1.237518

C 0 -3.609528 1.379181 -1.810242 C 0 0.255035 -0.338226 2.853348 H 0 0.646423 -0.881027 0.000015 H 0 -0.098633 2.140640 0.033646 H 0 0.988220 1.440109 -1.194702 H 0 1.493088 1.448288 0.496277 H 0 -0.201294 -2.778870 0.128464 H 0 -4.169235 -1.565109 0.912003 H 0 -2.362015 -2.361084 2.455566 H 0 -2.398514 -0.596405 2.441498 H 0 -0.977356 -4.926010 -0.022217 H 0 -1.972336 -4.180313 1.211975 H 0 -0.958710 -3.689285 -2.269669 H 0 -0.076538 -2.205917 -2.056839 H 0 -5.260666 -2.088242 -1.186996 H 0 0.089767 -2.393127 2.515533 H 0 -3.261139 -5.678207 -0.224960 H 0 -2.770767 -4.827759 -1.667786 H 0 -4.600845 -3.764175 0.544250 H 0 -5.071274 -4.328064 -1.048950 H 0 -1.843384 -1.901352 -3.674637 H 0 -2.021988 -0.826157 -2.309677 H 0 -4.156906 -1.571716 -3.079254 H 0 -3.735641 -3.260040 -2.974792 H 0 -6.570160 1.405121 -0.465256 H 0 -6.622025 -0.146713 0.382690 H 0 -6.479874 -0.103592 -1.378998 H 0 -4.301575 1.090698 2.156570 H 0 -4.362885 2.519806 1.119064 H 0 -2.823837 1.687256 1.388016 H 0 -2.526352 1.534988 -1.769730 H 0 -4.084152 2.367661 -1.866348 H 0 -3.836700 0.855835 -2.746063 H 0 -0.224197 0.636627 2.925552 H 0 1.302307 -0.387070 3.142670

B3LYP/6-31G* Energy = -1056.787709 B3LYP/6-31G* Free Energy = -1056.838661 B3LYP/6-31G* Free energy in solution = -1057.244034 Number of Imaginary Frequencies = 0 HOMO = -6.17 LUMO = -1.83

Complex (1-3)-ReSyn-BC

B3LYP/6-31G* Geometry O 0 -1.090958 1.222824 -2.422012 C 0 0.113052 1.077377 -2.698273 C 0 0.940231 2.228790 -3.165833 B 0 -2.050293 0.093658 -1.690536 C 0 -1.705490 -1.357941 -2.363525 C 0 -3.587418 0.650406 -1.794205 C 0 -1.454742 0.241989 -0.120316 C 0 -2.497055 -2.531662 -1.707443 C 0 -1.782608 -1.418961 -3.911774 C 0 -4.561798 -0.187042 -2.688843 Si 0 -3.850952 2.535507 -2.022141 C 0 0.000000 0.000000 0.000000 C 0 -3.898621 -2.229660 -1.138153 C 0 -4.945160 -1.552887 -2.041138 C 0 -3.181473 -1.492554 -4.526900 C 0 -4.127594 -0.339172 -4.172882 C 0 -2.859772 3.554000 -0.754532

S14

C 0 -3.438217 3.233429 -3.745500 C 0 -5.681564 2.949371 -1.690338 C 0 0.959885 0.946594 -0.000015

H 0 0.543793 0.074417 -2.729340 H 0 0.482086 3.179764 -2.886475 H 0 1.014465 2.180893 -4.262222 H 0 1.957184 2.161316 -2.769302 H 0 -0.648300 -1.582779 -2.140640 H 0 -3.987808 0.550507 -0.767593 H 0 -2.010284 -0.498444 0.468872 H 0 -1.712860 1.233322 0.266800 H 0 -2.568558 -3.364059 -2.423630 H 0 -1.906876 -2.928665 -0.869614 H 0 -1.221603 -2.302078 -4.256561 H 0 -1.261887 -0.553207 -4.349716 H 0 -5.510071 0.366028 -2.744339 H 0 0.323563 -1.042862 0.000000 H 0 -3.781708 -1.613693 -0.238449 H 0 -4.326752 -3.177841 -0.781784 H 0 -5.833038 -1.393768 -1.413300 H 0 -5.268372 -2.251328 -2.825729 H 0 -3.076553 -1.526733 -5.620911 H 0 -3.648956 -2.446335 -4.251480 H 0 -3.682983 0.603119 -4.517975 H 0 -5.040527 -0.475815 -4.770874 H 0 -3.124863 4.615555 -0.843292 H 0 -1.777924 3.469330 -0.903152 H 0 -3.079071 3.251297 0.276718 H 0 -2.411575 3.000259 -4.047745 H 0 -3.543686 4.326233 -3.739365 H 0 -4.110306 2.847534 -4.520325 H 0 -6.355713 2.513916 -2.436874 H 0 -5.836365 4.035858 -1.706955 H 0 -6.003600 2.587967 -0.705566 H 0 0.711731 2.005325 0.048645 H 0 2.016281 0.692780 0.047653 B3LYP/6-31G* Energy = -1056.786843 B3LYP/6-31G* Free Energy = -1056.837960 B3LYP/6-31G* Free energy in solution = -1057.243311 Number of Imaginary Frequencies = 0 HOMO = -6.16 LUMO = -1.81

Complex (1-3)-SiAnti-CB

B3LYP/6-31G* Geometry O 0 -0.231033 1.786392 -2.337036 C 0 -0.883163 0.803177 -2.716782 B 0 1.260269 1.742508 -1.567307 C 0 -2.288757 0.948196 -3.197891 C 0 2.143326 0.551254 -2.251800 C 0 1.798508 3.287598 -1.774719 C 0 3.494461 0.335281 -1.501129 C 0 2.340088 0.638077 -3.789261 C 0 3.212219 3.452957 -2.434143 Si 0 1.484207 4.591751 -0.404388 C 0 4.126450 1.563187 -0.815140 C 0 4.398163 2.829346 -1.645447 C 0 3.426727 1.589569 -4.296753 C 0 3.243149 3.066132 -3.938202 C 0 -0.388809 4.888397 -0.210434 C 0 2.203812 6.274017 -0.939697

C 0 2.220245 4.224700 1.312042 C 0 0.694672 1.312378 -0.045044 C 0 0.000000 0.000000 0.000000 C 0 -1.332703 -0.186768 0.000000 H 0 -0.399277 -0.173737 -2.796341 H 0 -2.693573 1.924683 -2.924728 H 0 -2.298492 0.847000 -4.292709 H 0 -2.915359 0.146225 -2.795776 H 0 1.592117 -0.392761 -2.105988 H 0 1.112183 3.700256 -2.537216 H 0 4.226974 -0.121750 -2.182571 H 0 3.340179 -0.411118 -0.709213 H 0 2.583344 -0.367233 -4.168045 H 0 1.390000 0.912400 -4.274582 H 0 3.421112 4.530563 -2.456848 H 0 5.079056 1.245500 -0.366745 H 0 3.493027 1.849991 0.031235 H 0 4.781464 3.581024 -0.940643 H 0 5.227921 2.644333 -2.342484 H 0 3.478271 1.504105 -5.391785 H 0 4.404602 1.248611 -3.933487 H 0 2.325821 3.444550 -4.413773 H 0 4.071930 3.619553 -4.404938 H 0 -0.937195 4.004715 0.132492 H 0 -0.832291 5.198425 -1.165253 H 0 -0.575134 5.692673 0.512741 H 0 1.864731 7.061890 -0.254776 H 0 1.878723 6.555359 -1.949203 H 0 3.300079 6.287048 -0.931076 H 0 1.753479 3.362320 1.799362 H 0 2.075668 5.091660 1.969894 H 0 3.298965 4.033493 1.260315 H 0 1.573273 1.282669 0.610870 H 0 0.030045 2.091049 0.343628 H 0 0.632996 -0.888702 -0.035583 H 0 -2.023422 0.651459 0.078964 H 0 -1.773956 -1.180695 0.000000 B3LYP/6-31G* Energy = -1056.782692 B3LYP/6-31G* Free Energy = -1056.834243 B3LYP/6-31G* Free energy in solution = -1057.237840 Number of Imaginary Frequencies = 0 HOMO = -6.06 LUMO = -1.81 Complex (1-3)-SiAnti-BC

B3LYP/6-31G* Geometry O 0 1.121567 0.525375 -0.000015 C 0 0.000000 0.000000 0.000000 C 0 -1.239166 0.821930 -0.123672 B 0 2.574402 -0.244080 0.354279 C 0 2.500610 -1.750137 -0.283096 C 0 3.680542 0.802887 -0.269455 C 0 2.423645 -0.259827 2.021362 C 0 3.664764 -2.651825 0.208496 C 0 2.315765 -1.856247 -1.827896 C 0 4.810410 0.129547 -1.116180 Si 0 4.338440 2.243973 0.805496 C 0 1.271454 -1.050537 2.526337 C 0 5.026932 -2.424423 -0.454712 C 0 5.587677 -0.998200 -0.381805 C 0 2.847366 -0.698746 -2.691589

S15

C 0 4.322784 -0.290070 -2.537170 C 0 5.484665 3.346313 -0.246887 C 0 5.336792 1.768616 2.354553 C 0 2.898926 3.377747 1.332840 C 0 0.082916 -0.549973 2.909760 H 0 -0.089844 -1.089859 0.000000 H 0 -1.019089 1.881363 0.022598 H 0 -1.662064 0.674606 -1.127700 H 0 -1.993378 0.483582 0.593826 H 0 1.611130 -2.236084 0.151886 H 0 3.106903 1.408142 -0.994553 H 0 3.364502 -0.678970 2.401611 H 0 2.358093 0.765839 2.397614 H 0 3.388779 -3.704803 0.042557 H 0 3.779068 -2.544983 1.296005 H 0 2.751175 -2.802734 -2.182037 H 0 1.242355 -1.944168 -2.056351 H 0 5.575714 0.893219 -1.307205 H 0 1.382278 -2.136505 2.517197 H 0 5.754211 -3.103775 0.012344 H 0 4.974609 -2.737000 -1.505676 H 0 5.716064 -0.714066 0.672073 H 0 6.602036 -1.031921 -0.805649 H 0 2.224380 0.185486 -2.505493 H 0 2.678436 -0.955185 -3.747696 H 0 4.476563 0.564392 -3.211136 H 0 4.970932 -1.086090 -2.929260 H 0 5.021072 3.622543 -1.202332 H 0 6.443298 2.865204 -0.473022 H 0 5.708405 4.277267 0.289658 H 0 5.712967 2.674698 2.847336 H 0 6.208618 1.153473 2.100998 H 0 4.743866 1.216309 3.090775 H 0 2.192749 2.896866 2.018097 H 0 2.328812 3.713486 0.457352 H 0 3.285507 4.273758 1.835098 H 0 -0.083557 0.523605 2.983994 H 0 -0.733566 -1.190994 3.233749 B3LYP/6-31G* Energy = -1056.783375000 B3LYP/6-31G* Free Energy = -1056.834713000 B3LYP/6-31G* Free energy in solution = -1057.238367 Number of Imaginary Frequencies = 0 HOMO = -6.02 LUMO = -1.86 TS-1+3-ReSyn-CB

B3LYP/6-31G* Geometry O 0 0.799393 1.126602 -0.581360 C 0 0.799393 2.392944 -0.581360 B 0 -0.495500 0.228500 -0.581360 C 0 2.100281 3.121658 -0.733749 C 0 -1.561400 0.803345 0.518738 C 0 -0.045807 -1.344711 -0.465912 C 0 -1.011490 0.537659 -2.218323 C 0 -2.944794 0.098923 0.483856 C 0 -0.987549 0.876053 1.967941 C 0 -0.596298 -2.140182 0.765533 Si 0 1.781570 -1.773880 -0.859283 C 0 -1.149689 1.966141 -2.431702 C 0 -3.048141 -1.247406 1.209259 C 0 -2.132034 -2.367157 0.704788

C 0 0.133224 -0.118179 2.322739 C 0 -0.132477 -1.625351 2.158615 C 0 1.979462 -3.669403 -0.887924 C 0 2.266754 -1.174423 -2.600845 C 0 3.093903 -1.116379 0.352539 C 0 -0.121414 2.801163 -2.758591 H 0 -0.036850 2.924637 -0.126480 H 0 2.772491 2.590866 -1.412018 H 0 2.583679 3.173233 0.252945 H 0 1.945129 4.145538 -1.082458 H 0 -1.798691 1.844772 0.242400 H 0 -0.524597 -1.844223 -1.329071 H 0 -1.958206 -0.001007 -2.315567 H 0 -0.261871 0.083954 -2.871613 H 0 -3.690720 0.769287 0.938065 H 0 -3.267471 -0.035187 -0.558914 H 0 -1.804871 0.789078 2.698471 H 0 -0.570847 1.880295 2.137360 H 0 -0.192368 -3.159424 0.686066 H 0 -2.092010 2.426819 -2.130386 H 0 -4.088028 -1.597107 1.136902 H 0 -2.869919 -1.094269 2.281509 H 0 -2.404648 -2.622177 -0.330063 H 0 -2.358490 -3.263107 1.302307 H 0 0.425797 0.056778 3.368561 H 0 1.015259 0.136688 1.725723 H 0 0.806198 -2.132523 2.421387 H 0 -0.856613 -1.956467 2.916672 H 0 2.975327 -3.942429 -1.259888 H 0 1.241684 -4.145538 -1.545868 H 0 1.870743 -4.118149 0.106369 H 0 1.582443 -1.556549 -3.368561 H 0 3.272400 -1.532211 -2.856583 H 0 2.275818 -0.081650 -2.675720 H 0 3.120941 -0.021988 0.374069 H 0 4.088013 -1.468400 0.047073 H 0 2.925385 -1.467056 1.377167 H 0 0.800339 2.408798 -3.180847 H 0 -0.268188 3.875641 -2.836044

B3LYP/6-31G* Energy = -1056.785926 B3LYP/6-31G* Free Energy = -1056.834743 B3LYP/6-31G* Free energy in solution = -1057.243731 Number of Imaginary Frequencies = 1 (-178.8)

TS-1+3-ReSyn-BC

B3LYP/6-31G* Geometry O 0 0.705109 1.131775 -0.736862 C 0 0.705109 2.397629 -0.736862 B 0 -0.584076 0.228043 -0.736862 C 0 2.005051 3.127090 -0.890700 C 0 -1.659470 0.801331 0.358734 C 0 -0.108521 -1.336044 -0.613205 C 0 -1.119644 0.539017 -2.368195 C 0 -3.020203 0.039429 0.374420 C 0 -1.085037 0.968216 1.791077 C 0 -0.541000 -2.074142 0.697830 Si 0 1.694580 -1.754700 -1.109344 C 0 -1.247314 1.969604 -2.584274 C 0 -3.017990 -1.453735 -0.008667 C 0 -2.062180 -2.414627 0.722092 C 0 -0.942337 -0.308212 2.624237

S16

C 0 -0.063614 -1.407715 2.017517 C 0 2.120651 -1.088684 -2.843170 C 0 3.050583 -1.147995 0.080582 C 0 1.879272 -3.648056 -1.230896 C 0 -0.219086 2.796860 -2.927261 H 0 -0.134109 2.931015 -0.290039 H 0 2.680527 2.591187 -1.561508 H 0 2.484497 3.188324 0.097366 H 0 1.849197 4.147629 -1.248749 H 0 -1.922180 1.829132 0.055573 H 0 -0.638947 -1.868179 -1.424774 H 0 -2.076889 0.016891 -2.450409 H 0 -0.389206 0.076462 -3.036087 H 0 -3.490036 0.159302 1.362350 H 0 -3.708740 0.533279 -0.326187 H 0 -1.732864 1.659821 2.352631 H 0 -0.100891 1.458786 1.742706 H 0 -0.040924 -3.053085 0.698471 H 0 -2.183884 2.438690 -2.278061 H 0 -2.817490 -1.535309 -1.083694 H 0 -4.041000 -1.835815 0.121277 H 0 -2.197525 -3.397110 0.248428 H 0 -2.390274 -2.549133 1.762192 H 0 -0.522720 -0.035782 3.603378 H 0 -1.938736 -0.714142 2.840027 H 0 0.950700 -1.013321 1.877350 H 0 0.026413 -2.202148 2.772934 H 0 3.120697 -1.429794 -3.140610 H 0 2.119736 0.006012 -2.880310 H 0 1.417038 -1.449951 -3.603378 H 0 2.995500 -0.066895 0.246872 H 0 4.041000 -1.372086 -0.336792 H 0 2.992400 -1.640259 1.058105 H 0 1.761795 -4.147629 -0.262253 H 0 2.873779 -3.911453 -1.613327 H 0 1.139740 -4.081436 -1.916061 H 0 0.699615 2.397964 -3.349960 H 0 -0.361359 3.871613 -3.009506 B3LYP/6-31G* Energy = -1056.786004 B3LYP/6-31G* Free Energy = -1056.835282 B3LYP/6-31G* Free energy in solution = -1057.242926 Number of Imaginary Frequencies = 1 (-168.2) TS-1+3-SiAnti-CB

B3LYP/6-31G* Geometry O 0 1.387451 1.421722 0.622742 C 0 1.387451 2.690506 0.622742 B 0 0.107849 0.518753 0.622742 C 0 2.698746 3.406418 0.759842 C 0 -1.003693 1.091690 -0.433289 C 0 0.680450 -1.008545 0.365265 C 0 -2.367447 0.339600 -0.367935 C 0 -0.490936 1.242798 -1.891388 C 0 0.059158 -1.788620 -0.844055 Si 0 1.071991 -2.162659 1.844498 C 0 -2.340118 -1.139572 0.062439 C 0 -1.452515 -2.126419 -0.714050 C 0 -0.465424 -0.025772 -2.748123 C 0 0.408203 -1.170074 -2.226044 C 0 2.475922 -1.413712 2.895569 C 0 1.759323 -3.820175 1.202133

C 0 -0.373535 -2.610214 3.001053 H 0 0.560074 3.224304 0.154266 H 0 3.371841 2.862122 1.426468 H 0 3.169495 3.456390 -0.232773 H 0 2.561661 4.430328 1.115891 H 0 -1.240936 2.124725 -0.128357 H 0 1.722549 -0.824951 0.043640 H 0 -2.886520 0.430634 -1.333450 H 0 -3.019700 0.855637 0.351212 H 0 -1.125793 1.976852 -2.412384 H 0 0.520554 1.677444 -1.885239 H 0 0.567368 -2.761429 -0.879379 H 0 -3.371841 -1.519470 0.033386 H 0 -2.044067 -1.188812 1.115631 H 0 -1.550430 -3.095291 -0.203888 H 0 -1.868881 -2.290100 -1.718246 H 0 -0.114502 0.243088 -3.754883 H 0 -1.491577 -0.389572 -2.887329 H 0 1.458954 -0.844696 -2.205200 H 0 0.360306 -1.979218 -2.970276 H 0 2.211578 -0.464600 3.374329 H 0 3.363510 -1.229904 2.277084 H 0 2.769241 -2.110900 3.690735 H 0 2.156219 -4.411194 2.037537 H 0 2.577484 -3.674118 0.485962 H 0 0.993973 -4.430328 0.708191 H 0 -0.780700 -1.746307 3.536987 H 0 -0.030869 -3.331116 3.754883 H 0 -1.200073 -3.081329 2.455353 C 0 -0.420380 0.855804 2.268616 C 0 -0.546967 2.288147 2.450714 C 0 0.492706 3.119431 2.757034 H 0 -1.374557 0.335403 2.375519 H 0 0.317184 0.421800 2.945023 H 0 -1.485306 2.753021 2.144241 H 0 1.407944 2.725113 3.191238 H 0 0.354600 4.195938 2.820602 B3LYP/6-31G* Energy = -1056.78054 B3LYP/6-31G* Free Energy = -1056.83005 B3LYP/6-31G* Free energy in solution = -1057.236962 Number of Imaginary Frequencies = 1 (-204.0) TS-1+3-SiAnti-BC

B3LYP/6-31G* Geometry O 0 1.463181 1.394989 0.405853 C 0 1.463181 2.663361 0.405853 B 0 0.182648 0.493088 0.405853 C 0 2.771149 3.379913 0.564529 C 0 -0.933060 1.082565 -0.645020 C 0 0.741882 -1.037170 0.156845 C 0 -2.345520 0.461761 -0.488525 C 0 -0.490097 1.106125 -2.141113 C 0 -0.073654 -1.878571 -0.878067 Si 0 1.355682 -2.095047 1.627365 C 0 -2.541016 -0.942398 -1.068283 C 0 -1.585831 -2.025909 -0.552597 C 0 0.525879 0.044464 -2.599000 C 0 0.195343 -1.437759 -2.350174 C 0 2.126328 -3.709900 0.969589 C 0 0.049713 -2.618988 2.910461 C 0 2.774400 -1.196930 2.530991

S17

H 0 0.641296 3.197098 -0.072708 H 0 3.432373 2.838165 1.245087 H 0 3.260315 3.427429 -0.419388 H 0 2.626617 4.404861 0.914764 H 0 -1.094482 2.139481 -0.374573 H 0 1.724792 -0.873657 -0.321869 H 0 -3.076400 1.124588 -0.977539 H 0 -2.628876 0.446945 0.573273 H 0 -1.381195 1.058243 -2.785187 H 0 -0.036209 2.083282 -2.364014 H 0 0.305237 -2.908264 -0.831650 H 0 -3.571289 -1.262390 -0.856491 H 0 -2.473312 -0.894379 -2.162720 H 0 -1.709000 -2.128220 0.534744 H 0 -1.925034 -2.980682 -0.980377 H 0 1.490585 0.267334 -2.126221 H 0 0.693222 0.175125 -3.678131 H 0 1.056946 -2.011078 -2.720078 H 0 -0.647934 -1.742233 -2.985840 H 0 2.854095 -3.519043 0.170883 H 0 1.377090 -4.404861 0.573196 H 0 2.656067 -4.230698 1.777634 H 0 0.515700 -3.250549 3.678131 H 0 -0.752228 -3.208984 2.450546 H 0 -0.416290 -1.770691 3.422714 H 0 2.464218 -0.274475 3.033859 H 0 3.571289 -0.930313 1.825516 H 0 3.215714 -1.852234 3.292725 C 0 -0.329453 0.806183 2.055359 C 0 -0.503540 2.233688 2.230759 C 0 0.513962 3.096542 2.526825 H 0 -1.255447 0.238541 2.174881 H 0 0.438385 0.403366 2.716812 H 0 -1.456192 2.667038 1.922363 H 0 1.437088 2.732254 2.970413 H 0 0.347153 4.169739 2.577484 B3LYP/6-31G* Energy = -1056.781045 B3LYP/6-31G* Free Energy = -1056.830549 B3LYP/6-31G* Free energy in solution = -1057.237341 Number of Imaginary Frequencies = 1 (-207.6) TS-1+3-ReAnti-CB

B3LYP/6-31G* Geometry C 0 2.650818 -2.451096 0.239029 C 0 2.642822 -0.895889 0.259796 C 0 1.279236 -3.147797 0.273804 C 0 0.310822 -2.807541 1.419052 B 0 1.321808 -0.212830 -0.427658 C 0 3.023300 -0.329468 1.652267 C 0 -0.153793 -0.460617 0.305450 C 0 -0.080002 -1.316589 1.624054 C 0 2.227219 -0.855774 2.846603 O 0 1.672821 1.309708 -0.443802 C 0 0.714493 -0.636978 2.775436 Si 0 -1.777405 -0.875290 -0.649796 C 0 0.929916 2.222702 -0.911865 C 0 -2.530075 0.706757 -1.416946 C 0 -3.141953 -1.463654 0.543396 C 0 -1.690262 -2.213821 -2.001877 C 0 1.444489 3.631012 -0.935867 H 0 3.275681 -2.832367 1.060440

H 0 3.148300 -2.793015 -0.679321 H 0 3.479950 -0.580231 -0.382385 H 0 0.767136 -2.942886 -0.673523 H 0 1.442947 -4.235367 0.284729 H 0 0.703064 -3.204941 2.365677 H 0 -0.607010 -3.382782 1.229126 H 0 4.086136 -0.551147 1.838593 H 0 2.947540 0.766678 1.624084 H 0 -0.441223 0.540771 0.683350 H 0 -1.100067 -1.345261 2.026062 H 0 2.430389 -1.926773 2.979095 H 0 2.602783 -0.374191 3.761078 H 0 0.287491 -1.001816 3.721664 H 0 0.504547 0.443115 2.751953 H 0 -0.150803 2.072540 -0.932404 H 0 -2.775192 1.432098 -0.629776 H 0 -3.471207 0.456192 -1.922882 H 0 -1.898880 1.217392 -2.151200 H 0 -2.925842 -2.438324 0.995178 H 0 -4.086151 -1.562347 -0.007751 H 0 -3.314362 -0.750824 1.358948 H 0 -2.692947 -2.364182 -2.422745 H 0 -1.366928 -3.177078 -1.590408 H 0 -1.021545 -1.973100 -2.834702 H 0 1.259964 4.082321 0.050018 H 0 2.521240 3.649704 -1.120071 H 0 0.922500 4.235382 -1.681686 C 0 1.482407 -0.515274 -2.155914 C 0 0.723587 0.439270 -2.938370 C 0 1.130890 1.713776 -3.215012 H 0 2.556519 -0.434921 -2.342987 H 0 1.158859 -1.546783 -2.310532 H 0 -0.307449 0.187119 -3.179000 H 0 2.177582 1.994247 -3.130554 H 0 0.490417 2.402084 -3.761078 B3LYP/6-31G* Energy = -1056.775091 B3LYP/6-31G* Free Energy = -1056.823079 B3LYP/6-31G* Free energy in solution = -1057.232856 Number of Imaginary Frequencies = 1 (-197.2) TS-1+3-ReAnti-BC

B3LYP/6-31G* Geometry C 0 2.423111 -1.555496 1.874222 C 0 1.453079 -2.193085 0.851044 C 0 3.406677 -0.523529 1.315018 C 0 2.776535 0.677246 0.601013 B 0 0.158371 -1.268951 0.453476 C 0 2.212234 -2.815826 -0.360733 C 0 0.425171 0.109848 -0.442062 C 0 1.949020 0.415283 -0.687943 C 0 2.162155 -2.037170 -1.683685 O 0 -0.757126 -2.271973 -0.316086 C 0 2.640213 -0.577621 -1.671570 Si 0 -0.507797 1.772797 -0.155106 C 0 -1.905289 -2.005585 -0.783218 C 0 0.290756 3.179413 -1.163696 C 0 -0.591980 2.426804 1.632492 C 0 -2.288895 1.705795 -0.848373 C 0 -2.691177 -3.106735 -1.431015 H 0 3.015579 -2.354309 2.346710 H 0 1.850143 -1.092987 2.691116

S18

H 0 1.013321 -3.049988 1.384537 H 0 4.107040 -1.020569 0.631287 H 0 4.026550 -0.145432 2.140625 H 0 3.595795 1.359894 0.331467 H 0 2.154831 1.230835 1.318634 H 0 3.262466 -2.999954 -0.088028 H 0 1.787781 -3.807892 -0.564819 H 0 0.033035 -0.134232 -1.449905 H 0 1.996521 1.372147 -1.219208 H 0 1.131653 -2.062103 -2.059662 H 0 2.757736 -2.580154 -2.432312 H 0 3.726563 -0.545547 -1.505875 H 0 2.493729 -0.192932 -2.691132 H 0 -2.140442 -0.978271 -1.065063 H 0 1.264832 3.487900 -0.768021 H 0 -0.363831 4.060287 -1.140000 H 0 0.433044 2.905975 -2.216568 H 0 0.407516 2.528900 2.071075 H 0 -1.183578 1.804764 2.311661 H 0 -1.045319 3.426620 1.629745 H 0 -2.753600 2.694443 -0.743027 H 0 -2.955902 0.987946 -0.360657 H 0 -2.277405 1.473969 -1.921600 H 0 -2.351517 -3.205002 -2.472504 H 0 -2.515579 -4.060287 -0.927400 H 0 -3.759827 -2.879623 -1.448776 C 0 -0.790161 -1.129150 1.931015 C 0 -2.191071 -0.886703 1.651260 C 0 -3.078018 -1.842361 1.240143 H 0 -0.635345 -2.083435 2.441956 H 0 -0.326553 -0.324295 2.505661 H 0 -2.526215 0.147949 1.600647 H 0 -2.869354 -2.898193 1.391922 H 0 -4.107056 -1.585495 1.000916 B3LYP/6-31G* Energy = -1056.775035 B3LYP/6-31G* Free Energy = -1056.824005 B3LYP/6-31G* Free energy in solution = -1057.232217 Number of Imaginary Frequencies = 1 (-207.6) TS-1+3-SiSyn-CB

B3LYP/6-31G* Geometry C 0 1.138107 -2.405487 -1.658615 C 0 1.163696 -0.859451 -1.683975 C 0 -0.247925 -3.053589 -1.633057 C 0 -1.155090 -2.639465 -0.471054 B 0 0.916275 -0.123627 -0.240311 C 0 0.309784 -0.288559 -2.855957 C 0 -0.586380 -0.250122 0.462677 C 0 -1.588257 -1.148712 -0.352737 C 0 -1.044403 0.332458 -2.478577 O 0 1.474777 1.319031 -0.525269 Si 0 -1.567535 1.198776 1.268204 C 0 -2.050354 -0.537689 -1.706009 C 0 1.621400 2.291138 0.268417 C 0 -3.315216 0.624878 1.763428 C 0 -0.809525 1.718552 2.947525 C 0 -1.847244 2.768188 0.219864 C 0 2.412277 3.480560 -0.188324 C 0 2.175461 -0.680466 0.832153 C 0 2.373825 0.261795 1.916200 C 0 3.187225 1.353989 1.845261

H 0 1.662521 -2.781677 -2.550903 H 0 1.719452 -2.773438 -0.801193 H 0 2.207123 -0.606705 -1.929031 H 0 -0.763779 -2.847672 -2.580231 H 0 -0.125992 -4.145905 -1.601593 H 0 -2.076492 -3.235168 -0.554016 H 0 -0.692581 -2.943649 0.480270 H 0 0.157852 -1.062271 -3.623505 H 0 0.885635 0.503082 -3.354340 H 0 -0.412125 -0.838593 1.383682 H 0 -2.500031 -1.219421 0.252609 H 0 -0.849808 1.238083 -1.892090 H 0 -1.537430 0.680100 -3.398422 H 0 -2.415527 -1.345261 -2.355957 H 0 -2.930603 0.094162 -1.516342 H 0 0.928024 2.426071 1.094208 H 0 -3.800262 1.410461 2.357147 H 0 -3.292603 -0.282547 2.379074 H 0 -3.959488 0.424622 0.900192 H 0 -0.772949 0.854263 3.623505 H 0 -1.461288 2.465302 3.419006 H 0 0.198868 2.145432 2.921280 H 0 -2.496170 2.553482 -0.636932 H 0 -0.935562 3.226868 -0.177185 H 0 -2.356796 3.526108 0.829208 H 0 1.743668 4.145889 -0.754059 H 0 3.225433 3.174973 -0.851044 H 0 2.806046 4.047379 0.658813 H 0 3.076263 -0.807343 0.223785 H 0 1.824066 -1.655685 1.180649 H 0 1.700043 0.191162 2.770920 H 0 3.959488 1.423508 1.082962 H 0 3.249756 2.068268 2.662613 B3LYP/6-31G* Energy = -1056.774124 B3LYP/6-31G* Free Energy = -1056.822644 B3LYP/6-31G* Free energy in solution = -1057.231894 Number of Imaginary Frequencies = 1 (-168.5) TS-1+3-SiSyn-BC

B3LYP/6-31G* Geometry C 0 2.311234 -2.521622 -0.305618 C 0 2.457245 -0.973251 -0.263672 C 0 0.892563 -3.089188 -0.481598 C 0 0.050507 -2.588547 -1.666000 B 0 1.177765 -0.156586 0.361938 C 0 2.993759 -0.406769 -1.602905 C 0 -0.292862 -0.320236 -0.397964 C 0 -0.201141 -1.054733 -1.790604 C 0 2.202118 -0.765610 -2.860291 O 0 1.762512 1.294617 0.480209 Si 0 -1.640442 1.045090 -0.554764 C 0 0.723267 -0.366302 -2.834793 C 0 1.250626 2.319687 1.012115 C 0 -3.187225 0.326782 -1.408905 C 0 -2.348740 1.643082 1.120255 C 0 -1.148285 2.580734 -1.574753 C 0 2.106171 3.536957 1.199600 H 0 2.962769 -2.930084 -1.092911 H 0 2.700775 -2.942413 0.631973 H 0 3.274338 -0.769348 0.446213 H 0 0.964279 -4.183853 -0.560059

S19

H 0 0.325592 -2.906723 0.440048 H 0 0.477402 -2.959808 -2.608124 H 0 -0.927979 -3.082092 -1.579391 H 0 4.027100 -0.761444 -1.745056 H 0 3.061020 0.687271 -1.523209 H 0 -0.852707 -1.021088 0.249649 H 0 -1.194107 -0.997528 -2.251709 H 0 2.674789 -0.279221 -3.725906 H 0 2.284943 -1.842972 -3.052673 H 0 0.309555 -0.581619 -3.831085 H 0 0.654922 0.723267 -2.713455 H 0 0.171509 2.451111 1.006363 H 0 -4.027100 1.024414 -1.296738 H 0 -3.492920 -0.626633 -0.960007 H 0 -3.049408 0.156616 -2.482100 H 0 -2.731277 0.793259 1.700134 H 0 -3.204697 2.299179 0.915802 H 0 -1.668900 2.200409 1.771927 H 0 -0.187515 3.021942 -1.287048 H 0 -1.914368 3.360840 -1.477341 H 0 -1.076843 2.329758 -2.639236 H 0 2.100861 4.111481 0.261627 H 0 3.139206 3.256638 1.418488 H 0 1.713211 4.183838 1.987686 C 0 1.123322 -0.564285 2.064240 C 0 0.472412 0.470093 2.845993 C 0 1.096024 1.594116 3.301880 H 0 2.166031 -0.703354 2.364426 H 0 0.597458 -1.521530 2.113449 H 0 -0.613190 0.429794 2.928940 H 0 2.180740 1.645050 3.356018 H 0 0.548950 2.370605 3.831100 B3LYP/6-31G* Energy = -1056.773095 B3LYP/6-31G* Free Energy = -1056.822311 B3LYP/6-31G* Free energy in solution = -1057.229972 Number of Imaginary Frequencies = 1 (-168.1)

Product P-1+3-S (Global minimum)

B3LYP/6-31G* Geometry C 0 0.025711 -0.997559 -2.748688 C 0 0.025711 0.544968 -2.748688 C 0 -1.324585 -1.741531 -2.748688 C 0 -0.704605 1.232376 -1.549179 C 0 -2.337006 -1.434296 -1.599700 C 0 -3.449783 -0.451492 -2.045181 B 0 -0.727539 0.236847 -0.301666 C 0 -1.637833 -1.057831 -0.261658 C 0 -2.108231 1.783234 -1.933472 C 0 -3.022537 0.849136 -2.734467 Si 0 -2.763000 -1.097687 1.302002 O 0 0.083893 0.397537 0.795334 C 0 -4.149811 -2.380554 1.094040 C 0 -1.714142 -1.620667 2.792618 C 0 -3.551468 0.586594 1.696426 C 0 1.073196 1.418213 0.991821 C 0 2.245972 0.783524 1.759811 C 0 0.456238 2.591431 1.749359 C 0 2.905029 -0.347855 1.019470 C 0 4.181656 -0.365982 0.633987 H 0 0.611389 -1.339249 -1.882751 H 0 0.591827 -1.337830 -3.627029

H 0 -0.380661 0.918320 -3.698807 H 0 1.078461 0.856491 -2.737228 H 0 -1.825165 -1.589508 -3.715378 H 0 -1.083145 -2.812714 -2.712662 H 0 -0.116776 2.123520 -1.293106 H 0 -2.867584 -2.379837 -1.423965 H 0 -4.080765 -0.207169 -1.180008 H 0 -4.104675 -0.990585 -2.745026 H 0 -0.938583 -1.877655 -0.015213 H 0 -1.961105 2.691635 -2.536072 H 0 -2.635406 2.112991 -1.025894 H 0 -3.930832 1.407654 -3.000824 H 0 -2.541626 0.608032 -3.690842 H 0 -4.722656 -2.469620 2.025894 H 0 -4.856125 -2.117676 0.298569 H 0 -3.745270 -3.373672 0.863342 H 0 -2.307724 -1.608551 3.715378 H 0 -1.321243 -2.637268 2.666214 H 0 -0.860031 -0.949265 2.925598 H 0 -2.788696 1.365936 1.812973 H 0 -4.248581 0.917114 0.917892 H 0 -4.112473 0.535126 2.638138 H 0 1.443802 1.761292 0.018463 H 0 2.982712 1.566315 1.979660 H 0 1.856445 0.422729 2.723206 H 0 0.064865 2.257553 2.716919 H 0 1.202515 3.373672 1.929062 H 0 -0.368668 3.031448 1.178986 H 0 2.264328 -1.198914 0.791565 H 0 4.606308 -1.210831 0.098114 H 0 4.856125 0.462265 0.844482 B3LYP/6-31G* Energy = -1056.854484 B3LYP/6-31G* Free Energy = -1056.908071 B3LYP/6-31G* Free energy in solution = -1057.308617 Number of Imaginary Frequencies = 0 Product P-1+3-S (from IRC of TS-1+3-ReSyn-CB)

B3LYP/6-31G* Geometry O 0 0.595734 1.128433 0.565887 C 0 0.595734 2.557297 0.565887 B 0 -0.469925 0.263504 0.565887 C 0 1.496414 3.034317 1.702881 C 0 -1.992752 0.740082 0.667206 C 0 -0.070938 -1.265366 0.403275 C 0 1.090469 3.048355 -0.808975 C 0 -2.800354 0.336060 -0.604340 C 0 -2.672760 0.265457 1.988251 C 0 -1.241119 -2.288055 0.507278 Si 0 1.555649 -1.779526 1.298874 C 0 0.152908 2.725449 -1.939255 C 0 -3.295685 -1.113129 -0.674423 C 0 -2.222290 -2.206879 -0.691666 C 0 -2.046570 -0.965546 2.668686 C 0 -1.970123 -2.289703 1.883347 C 0 1.689774 -3.675964 1.349213 C 0 3.036697 -1.136230 0.302216 C 0 1.719345 -1.151108 3.084717 C 0 0.434082 1.915955 -2.961624 H 0 -0.421005 2.933380 0.732681 H 0 2.520691 2.672348 1.561050 H 0 1.131210 2.658569 2.664200

S20

H 0 1.517487 4.128937 1.746414 H 0 -2.031586 1.837021 0.679916 H 0 0.282318 -1.311905 -0.645462 H 0 2.078110 2.609787 -0.998047 H 0 1.224411 4.138245 -0.743774 H 0 -3.684418 0.988098 -0.664307 H 0 -2.203018 0.558792 -1.500412 H 0 -3.744995 0.094574 1.818344 H 0 -2.621506 1.084976 2.717590 H 0 -0.801163 -3.289261 0.410034 H 0 -0.828934 3.200546 -1.895157 H 0 -3.905350 -1.220474 -1.582657 H 0 -3.985184 -1.300812 0.158722 H 0 -1.630798 -2.119324 -1.615067 H 0 -2.743958 -3.172836 -0.761307 H 0 -2.599396 -1.161789 3.598251 H 0 -1.031982 -0.694595 2.989075 H 0 -1.463593 -3.008408 2.542603 H 0 -2.983688 -2.691895 1.745743 H 0 2.656082 -3.972153 1.777100 H 0 1.627991 -4.114914 0.345840 H 0 0.906693 -4.138260 1.961807 H 0 3.031326 -1.535141 -0.720093 H 0 3.985168 -1.433838 0.766769 H 0 3.016556 -0.044220 0.233688 H 0 1.619308 -0.061584 3.141907 H 0 2.708420 -1.413452 3.481659 H 0 0.973038 -1.594376 3.754211 H 0 -0.284210 1.723602 -3.754227 H 0 1.399109 1.420914 -3.047867 B3LYP/6-31G* Energy = -1056.852674 B3LYP/6-31G* Free Energy = -1056.905948 B3LYP/6-31G* Free energy in solution = -1057.307731 Number of Imaginary Frequencies = 0 Product P-1+3-R (Global minimum) B3LYP/6-31G* Geometry C 0 0.861786 -1.297516 -3.081512 C 0 0.861786 0.243393 -3.081512 C 0 -0.491608 -2.033142 -3.081512 C 0 0.139343 0.939484 -1.881653 C 0 -1.494415 -1.723129 -1.926605 C 0 -2.606689 -0.733231 -2.358215 B 0 0.084518 -0.028915 -0.613342 C 0 -0.790161 -1.350586 -0.590912 C 0 -1.260330 1.501648 -2.266830 C 0 -2.186188 0.567047 -3.054321 Si 0 -1.907166 -1.455994 0.976669 O 0 0.811783 0.190445 0.530670 C 0 -2.708435 0.206055 1.435516 C 0 -3.288910 -2.737671 0.727386 C 0 -0.851761 -2.036652 2.440659 C 0 1.739243 1.256226 0.779526 C 0 1.690720 1.547806 2.290588 C 0 3.128265 0.846542 0.298248 C 0 2.465134 2.774765 2.687027 C 0 3.480423 2.799759 3.551544 H 0 1.445282 -1.642426 -2.215698 H 0 1.426041 -1.638367 -3.960907 H 0 0.448715 0.614090 -4.029922 H 0 1.913956 0.557800 -3.081726

H 0 -0.257889 -3.106171 -3.051666 H 0 -0.995148 -1.872300 -4.045288 H 0 0.738937 1.825653 -1.636185 H 0 -2.028824 -2.666336 -1.751282 H 0 -3.222992 -0.484924 -1.483582 H 0 -3.275665 -1.268097 -3.047882 H 0 -0.064026 -2.152725 -0.363403 H 0 -1.107330 2.402954 -2.878525 H 0 -1.780700 1.845261 -1.360123 H 0 -3.097687 1.125839 -3.308670 H 0 -1.719055 0.325302 -4.017395 H 0 -3.277100 0.111618 2.369278 H 0 -1.949829 0.982391 1.590042 H 0 -3.401688 0.565872 0.666077 H 0 -3.864807 -2.852585 1.654556 H 0 -3.993164 -2.456177 -0.063538 H 0 -2.880890 -3.723495 0.472427 H 0 -1.448273 -2.095169 3.359695 H 0 -0.432800 -3.033783 2.255478 H 0 -0.015808 -1.352982 2.617462 H 0 1.416733 2.157242 0.241852 H 0 0.633530 1.676651 2.562958 H 0 2.056671 0.669556 2.837006 H 0 3.864578 1.619217 0.541473 H 0 3.433228 -0.087418 0.783936 H 0 3.134995 0.687805 -0.785263 H 0 2.146881 3.709290 2.220261 H 0 3.993149 3.723511 3.806122 H 0 3.832733 1.896255 4.045303 B3LYP/6-31G* Energy = -1056.853870 B3LYP/6-31G* Free Energy = -1056.907945 B3LYP/6-31G* Free energy in solution = -1057.309255 Number of Imaginary Frequencies = 0 Product P-1+3-R (from IRC of TS-1+3-SiAnti-BC)

B3LYP/6-31G* Geometry O 0 0.812622 1.220810 -0.646790 C 0 0.812622 2.650650 -0.646790 B 0 -0.264130 0.368774 -0.646790 C 0 1.639694 3.108795 -1.847794 C 0 -1.773697 0.867477 -0.494858 C 0 0.102020 -1.151581 -0.909760 C 0 1.392532 3.173996 0.679214 C 0 -2.566498 0.111252 0.610245 C 0 -2.481873 0.830063 -1.887634 C 0 -1.095078 -2.084473 -1.258728 Si 0 1.344604 -1.872726 0.373581 C 0 0.524902 2.920044 1.881058 C 0 -3.105530 -1.277802 0.249573 C 0 -2.065430 -2.354385 -0.081818 C 0 -1.895691 -0.158539 -2.915726 C 0 -1.848236 -1.657562 -2.557861 C 0 1.444092 -3.762100 0.190491 C 0 0.903931 -1.469437 2.176468 C 0 3.066025 -1.166595 0.008682 C 0 0.922745 2.320740 3.004379 H 0 -0.213440 3.024231 -0.756195 H 0 2.670563 2.747696 -1.762512 H 0 1.216949 2.713455 -2.777023 H 0 1.657547 4.202423 -1.913773 H 0 -1.778412 1.915482 -0.168015

S21

H 0 0.756912 -1.114807 -1.799789 H 0 2.387527 2.736069 0.827942 H 0 1.533600 4.259506 0.563141 H 0 -3.430100 0.732620 0.890366 H 0 -1.949066 0.036774 1.517212 H 0 -3.556442 0.640945 -1.758255 H 0 -2.413574 1.829117 -2.338989 H 0 -0.669250 -3.070526 -1.488174 H 0 -0.501419 3.285614 1.811798 H 0 -3.710251 -1.637939 1.093689 H 0 -3.808273 -1.185349 -0.588638 H 0 -1.481094 -2.575500 0.821000 H 0 -2.615372 -3.278580 -0.311722 H 0 -0.875824 0.170319 -3.164261 H 0 -2.464447 -0.058090 -3.850754 H 0 -1.369644 -2.159286 -3.410095 H 0 -2.871948 -2.056641 -2.524460 H 0 1.709900 -4.054367 -0.832840 H 0 0.500732 -4.259506 0.442886 H 0 2.216415 -4.165588 0.857620 H 0 1.697495 -1.821686 2.848083 H 0 -0.029526 -1.946289 2.496582 H 0 0.796051 -0.389481 2.329651 H 0 3.061661 -0.073868 0.068451 H 0 3.401978 -1.440506 -0.999252 H 0 3.808273 -1.549255 0.720383 H 0 0.254242 2.187653 3.850769 H 0 1.937592 1.946640 3.122986 B3LYP/6-31G* Energy = -1056.853353 B3LYP/6-31G* Free Energy = -1056.906194 B3LYP/6-31G* Free energy in solution = -1057.308812 Number of Imaginary Frequencies = 0

Allylboration Reaction between 2 and 3

Complex (2-3)-ReSyn-CB

B3LYP/6-31G* Geometry O 0 -1.397537 1.103134 -2.300613 C 0 -0.198792 1.197037 -2.623535 C 0 0.365067 2.506958 -3.062469 B 0 -2.086624 -0.188766 -1.629500 C 0 -1.577087 -1.529968 -2.407745 C 0 -3.718979 0.076233 -1.600006 C 0 -1.475998 -0.027634 -0.065948 C 0 -2.186523 -2.834579 -1.817627 C 0 -1.722809 -1.473450 -3.959656 C 0 -4.604965 -0.804382 -2.545670 C 0 -4.115311 1.546402 -1.583115 C 0 0.000000 0.000000 0.000000 C 0 -3.585327 -3.231293 -2.308990 C 0 -4.729568 -2.255188 -2.008698 C 0 -2.833588 -0.568832 -4.526489 C 0 -4.286453 -0.793533 -4.070084 C 0 -4.242325 2.332413 -2.742569 C 0 -4.371262 2.184906 -0.356216 C 0 0.763580 1.111908 0.000000 C 0 -4.721771 3.533829 -0.282623 C 0 -4.601563 3.679443 -2.678192 C 0 -4.839813 4.292435 -1.447189 H 0 0.407639 0.294922 -2.728317 H 0 -0.265656 3.330978 -2.722672

H 0 0.400574 2.518982 -4.161896 H 0 1.390594 2.630692 -2.703583 H 0 -0.496460 -1.638428 -2.212967 H 0 -3.999420 -0.283417 -0.598923 H 0 -1.871964 -0.883835 0.494888 H 0 -1.900131 0.884232 0.370346 H 0 -1.514511 -3.672700 -2.057022 H 0 -2.198959 -2.772919 -0.719772 H 0 -1.834930 -2.490311 -4.361800 H 0 -0.779587 -1.111038 -4.396744 H 0 -5.622269 -0.396271 -2.455368 H 0 0.511856 -0.963089 -0.054000 H 0 -3.841553 -4.201538 -1.859970 H 0 -3.547028 -3.417816 -3.390167 H 0 -4.894135 -2.213440 -0.922104 H 0 -5.646896 -2.689072 -2.432556 H 0 -2.815460 -0.655884 -5.622864 H 0 -2.565918 0.473053 -4.315140 H 0 -4.886353 -0.008011 -4.547958 H 0 -4.657990 -1.733063 -4.503174 H 0 -4.062073 1.889740 -3.716049 H 0 -4.304672 1.605255 0.562134 H 0 0.320465 2.101044 0.099014 H 0 1.849930 1.062531 0.000000 H 0 -4.913712 3.987473 0.687057 H 0 -4.696411 4.252335 -3.598114 H 0 -5.120361 5.341446 -1.397705 B3LYP/6-31G* Energy = -879.186337 B3LYP/6-31G* Free Energy = -879.234509 B3LYP/6-31G* Free energy in solution = -879.629051 Number of Imaginary Frequencies = 0 HOMO = -5.7 LUMO = -1.8 Complex (2-3)-ReSyn-BC

B3LYP/6-31G* Geometry O 0 -1.140594 0.504059 0.000000 C 0 0.000000 0.000000 0.000000 B 0 -2.499084 -0.229904 0.414551 C 0 1.200607 0.858627 -0.224869 C 0 -2.519974 -1.716125 -0.267929 C 0 -3.748520 0.790298 0.050278 C 0 -2.284927 -0.244171 2.094894 C 0 -3.778656 -2.562805 0.092896 C 0 -2.251205 -1.729584 -1.797592 C 0 -4.688873 0.343689 -1.122391 C 0 -3.396774 2.272873 -0.012817 C 0 -1.038696 -0.908981 2.518158 C 0 -5.099457 -1.816406 0.367508 C 0 -5.633743 -0.813049 -0.674911 C 0 -3.419128 -1.341003 -2.710358 C 0 -4.022690 0.052170 -2.491302 C 0 -3.933441 3.151886 0.944672 C 0 -2.563995 2.842529 -0.994293 C 0 0.145706 -0.295242 2.727493 C 0 -2.296158 4.211426 -1.023590 C 0 -3.662277 4.521332 0.929413 C 0 -2.842072 5.061676 -0.060287 H 0 0.116577 -1.085403 0.000031 H 0 1.488327 0.782578 -1.283966 H 0 2.049835 0.508591 0.368179

S22

H 0 0.975220 1.902908 0.001572 H 0 -1.674316 -2.283630 0.158096 H 0 -4.397980 0.719604 0.934540 H 0 -3.159790 -0.767532 2.498947 H 0 -2.316925 0.794693 2.444336 H 0 -3.943848 -3.315567 -0.692429 H 0 -3.563431 -3.143677 1.000687 H 0 -1.932663 -2.743240 -2.087891 H 0 -1.397675 -1.076706 -2.036789 H 0 -5.347046 1.202576 -1.316086 H 0 -1.054672 -2.000015 2.560181 H 0 -5.882416 -2.570358 0.533493 H 0 -5.004715 -1.291931 1.326141 H 0 -6.533188 -0.364090 -0.231339 H 0 -5.989624 -1.354309 -1.562195 H 0 -3.075684 -1.404526 -3.752945 H 0 -4.210876 -2.095795 -2.622345 H 0 -3.264069 0.815247 -2.702637 H 0 -4.795227 0.192307 -3.261490 H 0 -4.585114 2.750793 1.718338 H 0 -2.103806 2.206848 -1.742874 H 0 0.221909 0.789993 2.752823 H 0 1.042633 -0.852676 2.986984 H 0 -1.652908 4.614716 -1.802689 H 0 -4.098053 5.164932 1.690079 H 0 -2.630325 6.127609 -0.081772 B3LYP/6-31G* Energy = -879.185585 B3LYP/6-31G* Free Energy = -879.234304 B3LYP/6-31G* Free energy in solution = -879.628203 Number of Imaginary Frequencies = 0 HOMO = -5.8 LUMO = -1.8

Complex (2-3)-SiAnti-CB

B3LYP/6-31G* Geometry O 0 0.704361 1.672302 -2.339493 C 0 -0.362869 1.168503 -2.718002 C 0 -1.493744 2.018372 -3.193497 B 0 1.953613 0.854858 -1.560410 C 0 2.128708 -0.586334 -2.295822 C 0 3.203766 1.925858 -1.739578 C 0 1.250504 0.799316 -0.050064 C 0 3.135100 -1.505646 -1.538269 C 0 2.422928 -0.529541 -3.822464 C 0 4.557938 1.353455 -2.283707 C 0 3.371704 2.895600 -0.577621 C 0 0.000000 0.000000 0.000000 C 0 4.285751 -0.819382 -0.774948 C 0 5.206619 0.153275 -1.529861 C 0 3.871400 -0.264100 -4.250122 C 0 4.484421 1.068863 -3.807495 C 0 2.641602 4.098663 -0.575653 C 0 4.213287 2.662567 0.523132 C 0 -1.250534 0.497086 0.000000 C 0 4.319855 3.582474 1.569031 C 0 2.738358 5.018646 0.467697 C 0 3.582840 4.766083 1.550385 H 0 -0.453934 0.082184 -2.798538 H 0 -1.569641 1.925858 -4.286377 H 0 -2.440140 1.661987 -2.775055 H 0 -1.329926 3.065689 -2.931885

H 0 1.163818 -1.116135 -2.226028 H 0 2.858826 2.564224 -2.565353 H 0 1.995392 0.370865 0.632187 H 0 1.061523 1.821686 0.294998 H 0 3.550064 -2.249710 -2.233734 H 0 2.580414 -2.091812 -0.792358 H 0 2.128036 -1.491806 -4.269547 H 0 1.778198 0.225571 -4.298706 H 0 5.275879 2.181503 -2.196320 H 0 0.112106 -1.085770 -0.035721 H 0 4.917404 -1.607651 -0.340286 H 0 3.861450 -0.286697 0.083755 H 0 5.921692 0.542435 -0.793457 H 0 5.823257 -0.410370 -2.243820 H 0 4.504761 -1.088272 -3.898270 H 0 3.919220 -0.313477 -5.347443 H 0 3.949921 1.895782 -4.298004 H 0 5.510574 1.101791 -4.201523 H 0 1.983932 4.312820 -1.415680 H 0 4.800323 1.751923 0.570969 H 0 -1.433456 1.567444 0.080826 H 0 -2.126511 -0.147476 0.000000 H 0 4.985336 3.369247 2.402481 H 0 2.159882 5.939056 0.430069 H 0 3.667603 5.482300 2.363510 B3LYP/6-31G* Energy = -879.18517 B3LYP/6-31G* Free Energy = -879.234648 B3LYP/6-31G* Free energy in solution = -879.627947 Number of Imaginary Frequencies = 0 HOMO = -5.7 LUMO = -1.9 Complex (2-3)-SiAnti-BC

B3LYP/6-31G* Geometry O 0 1.177994 0.385971 0.000015 C 0 0.000000 0.000000 0.000000 C 0 -1.131027 0.964371 -0.128800 B 0 2.519424 -0.550980 0.372086 C 0 2.291229 -2.017822 -0.315231 C 0 3.760910 0.378983 -0.206192 C 0 2.360184 -0.545227 2.029358 C 0 3.277542 -3.086441 0.225372 C 0 2.211838 -2.072769 -1.872284 C 0 4.878600 -0.439804 -0.918594 C 0 4.277771 1.436630 0.764496 C 0 1.126968 -1.213470 2.514938 C 0 4.702332 -3.021622 -0.330673 C 0 5.424026 -1.679413 -0.148911 C 0 2.976303 -1.004837 -2.677551 C 0 4.472977 -0.777542 -2.385727 C 0 3.522034 2.610504 0.951523 C 0 5.475342 1.333817 1.490341 C 0 -0.007202 -0.588943 2.883118 C 0 5.890808 2.343628 2.363342 C 0 3.928300 3.619232 1.822693 C 0 5.120529 3.491562 2.538956 H 0 -0.220398 -1.070526 0.000000 H 0 -1.561081 0.871796 -1.136322 H 0 -1.925095 0.715591 0.582200 H 0 -0.788940 1.990005 0.023209 H 0 1.312897 -2.383743 0.039963

S23

H 0 3.297592 0.975708 -1.003372 H 0 3.252731 -1.049393 2.424545 H 0 2.398956 0.488556 2.387405 H 0 2.874985 -4.085480 -0.002930 H 0 3.322098 -3.027817 1.321442 H 0 2.521027 -3.072952 -2.211487 H 0 1.158508 -1.990219 -2.180847 H 0 5.743088 0.233047 -1.003860 H 0 1.120285 -2.305298 2.497971 H 0 5.301453 -3.801529 0.160080 H 0 4.692017 -3.290802 -1.394455 H 0 5.470505 -1.456192 0.924652 H 0 6.466324 -1.826645 -0.467255 H 0 2.452866 -0.047623 -2.560043 H 0 2.879440 -1.252716 -3.744598 H 0 4.785187 0.060623 -3.023666 H 0 5.053741 -1.640823 -2.737381 H 0 2.595444 2.728836 0.394272 H 0 6.109512 0.461838 1.372833 H 0 -0.053574 0.495621 2.966766 H 0 -0.893707 -1.139038 3.190140 H 0 6.826706 2.228027 2.905319 H 0 3.317734 4.512589 1.934677 H 0 5.445251 4.277115 3.216263 B3LYP/6-31G* Energy = -879.1855 B3LYP/6-31G* Free Energy = -879.234822 B3LYP/6-31G* Free energy in solution = -879.627933 Number of Imaginary Frequencies = 0 HOMO = -5.6 LUMO = -1.9 TS-2+3-ReSyn-CB

B3LYP/6-31G* Geometry O 0 0.218872 0.784973 -0.072861 C 0 0.207779 2.048462 0.009918 B 0 -1.039734 -0.117691 -0.012970 C 0 1.490662 2.793045 -0.201569 C 0 -2.010895 0.310608 1.228729 C 0 -0.570343 -1.701645 -0.071060 C 0 -3.309250 -0.539429 1.329346 C 0 -1.266159 0.393800 2.597397 C 0 -0.775345 -2.548965 1.232620 C 0 0.781158 -1.925934 -0.734528 C 0 -3.200562 -1.890945 2.048203 C 0 -2.265945 -2.934219 1.424820 C 0 -0.021332 -0.498200 2.769058 C 0 -0.152283 -2.017868 2.557785 C 0 2.009400 -1.757187 -0.070100 C 0 0.840118 -2.320984 -2.082886 C 0 2.053864 -2.527298 -2.741043 C 0 3.226456 -1.970871 -0.717972 C 0 3.258530 -2.353622 -2.060226 C 0 -1.722610 0.275711 -1.566100 C 0 -1.885910 1.713043 -1.682266 C 0 -0.893661 2.573807 -2.050583 H 0 -0.591309 2.540955 0.565598 H 0 2.117477 2.282837 -0.936584 H 0 2.036118 2.817123 0.753403 H 0 1.309311 3.826355 -0.507141 H 0 -2.381210 1.329941 1.027313 H 0 -1.289368 -2.152512 -0.770523

H 0 -4.069260 0.047531 1.867203 H 0 -3.724274 -0.703384 0.323868 H 0 -1.971573 0.206528 3.419388 H 0 -0.925583 1.427780 2.757767 H 0 -0.273926 -3.507996 1.036865 H 0 -4.207214 -2.328918 2.105713 H 0 -2.902481 -1.720108 3.090805 H 0 -2.673111 -3.251312 0.453552 H 0 -2.298874 -3.826340 2.067123 H 0 0.371811 -0.340317 3.784134 H 0 0.757600 -0.123611 2.095154 H 0 0.859756 -2.431854 2.657593 H 0 -0.716995 -2.450867 3.395721 H 0 2.020600 -1.455292 0.971527 H 0 -0.089462 -2.483185 -2.624786 H 0 2.054855 -2.835434 -3.784134 H 0 4.155838 -1.836731 -0.168808 H 0 4.207214 -2.520172 -2.564056 H 0 -2.673569 -0.263855 -1.602844 H 0 -1.033951 -0.132370 -2.311646 H 0 -2.799149 2.147217 -1.271469 H 0 -0.010559 2.212967 -2.571700 H 0 -1.050034 3.649765 -2.051697 B3LYP/6-31G* Energy = -879.18538 B3LYP/6-31G* Free Energy = -879.232085 B3LYP/6-31G* Free energy in solution = -879.628657 Number of Imaginary Frequencies = 1 (-169.5) TS-2+3-ReSyn-BC B3LYP/6-31G* Geometry O 0 0.242859 0.825333 -0.428894 C 0 0.242950 2.085022 -0.332794 B 0 -1.014969 -0.085770 -0.386887 C 0 1.527084 2.825211 -0.547485 C 0 -1.978546 0.346832 0.864624 C 0 -0.525497 -1.662400 -0.461212 C 0 -3.301498 -0.469177 0.986389 C 0 -1.234421 0.423400 2.225632 C 0 -0.732407 -2.504089 0.845718 C 0 0.838303 -1.897537 -1.100998 C 0 -3.301208 -1.931625 0.496414 C 0 -2.228165 -2.906509 1.022873 C 0 -0.951889 -0.904892 2.934540 C 0 -0.125168 -1.934921 2.153763 C 0 0.919571 -2.607971 -2.311920 C 0 2.053894 -1.456284 -0.545502 C 0 3.278214 -1.722900 -1.158890 C 0 2.139648 -2.869766 -2.938187 C 0 3.330536 -2.430206 -2.361481 C 0 -1.694000 0.319305 -1.932449 C 0 -1.860809 1.759445 -2.047165 C 0 -0.879547 2.623352 -2.429092 H 0 -0.561981 2.584839 0.207184 H 0 2.066757 2.865097 0.410324 H 0 1.347519 3.853912 -0.869141 H 0 2.157059 2.302841 -1.271118 H 0 -2.308304 1.383987 0.680618 H 0 -1.225082 -2.122559 -1.172806 H 0 -3.648682 -0.437576 2.030060 H 0 -4.086349 0.043381 0.412369 H 0 -1.828827 1.042664 2.916061

S24

H 0 -0.280579 0.957550 2.100616 H 0 -0.191437 -3.446045 0.678452 H 0 -4.284897 -2.363480 0.730804 H 0 -3.249054 -1.927551 -0.599365 H 0 -2.390381 -3.853897 0.490356 H 0 -2.421005 -3.133011 2.080307 H 0 -0.425415 -0.686737 3.874832 H 0 -1.903244 -1.360504 3.237122 H 0 0.871307 -1.524200 1.950668 H 0 0.044861 -2.787506 2.827515 H 0 0.001526 -2.969833 -2.770935 H 0 2.046249 -0.880798 0.373444 H 0 4.197235 -1.370453 -0.695511 H 0 2.156662 -3.422333 -3.874817 H 0 4.284897 -2.634018 -2.840408 H 0 -2.647141 -0.216232 -1.974228 H 0 -1.008987 -0.086000 -2.683792 H 0 -2.774063 2.190155 -1.632400 H 0 0.008698 2.265320 -2.943817 H 0 -1.039505 3.698807 -2.429443 B3LYP/6-31G* Energy = -879.184979 B3LYP/6-31G* Free Energy = -879.232049 B3LYP/6-31G* Free energy in solution = -879.628115 Number of Imaginary Frequencies = 1 (-138.2) TS-2+3-SiAnti-CB B3LYP/6-31G* Geometry O 0 1.408798 1.107941 -0.192780 C 0 1.405991 2.373123 -0.281540 B 0 0.124664 0.204803 -0.220139 C 0 2.697342 3.109680 -0.083038 C 0 -0.867874 0.660919 -1.430878 C 0 0.735138 -1.339294 -0.310349 C 0 -2.258682 -0.039185 -1.391617 C 0 -0.214233 0.597961 -2.841522 C 0 0.126923 -2.285339 -1.400665 C 0 0.971878 -2.011887 1.033844 C 0 -2.324997 -1.460770 -0.798721 C 0 -1.408768 -2.549591 -1.378448 C 0 -0.178177 -0.767822 -3.538010 C 0 0.594498 -1.883789 -2.825531 C 0 2.160339 -1.734161 1.736221 C 0 0.067062 -2.896271 1.644638 C 0 0.334564 -3.471466 2.889709 C 0 2.430725 -2.299637 2.981537 C 0 1.516251 -3.176880 3.568375 C 0 -0.497940 0.626617 1.347885 C 0 -0.675308 2.065033 1.412155 C 0 0.316559 2.946121 1.736069 H 0 0.618057 2.866196 -0.851822 H 0 3.253525 3.091949 -1.031693 H 0 2.525635 4.155426 0.183197 H 0 3.311203 2.622665 0.678314 H 0 -1.092316 1.731506 -1.289230 H 0 1.750214 -1.152283 -0.688232 H 0 -2.697510 -0.045700 -2.400269 H 0 -2.943649 0.575409 -0.790222 H 0 -0.758972 1.283447 -3.509521 H 0 0.813034 0.990051 -2.788788 H 0 0.598312 -3.263351 -1.225922 H 0 -3.362762 -1.813644 -0.888474

H 0 -2.135605 -1.399948 0.278961 H 0 -1.604233 -3.463638 -0.802750 H 0 -1.734039 -2.791595 -2.399994 H 0 -1.207169 -1.101837 -3.722641 H 0 0.263123 -0.632156 -4.535812 H 0 1.661713 -1.620560 -2.787582 H 0 0.530304 -2.779541 -3.460358 H 0 2.884750 -1.057037 1.288406 H 0 -0.861893 -3.149384 1.145889 H 0 -0.388565 -4.155411 3.328247 H 0 3.362747 -2.062805 3.489975 H 0 1.724487 -3.626465 4.535812 H 0 -1.439697 0.082825 1.452881 H 0 0.219543 0.259705 2.084793 H 0 -1.598709 2.477844 1.001877 H 0 1.200317 2.609787 2.272263 H 0 0.151505 4.020386 1.704071 B3LYP/6-31G* Energy = -879.182976 B3LYP/6-31G* Free Energy = -879.229789 B3LYP/6-31G* Free energy in solution = -879.627178 Number of Imaginary Frequencies = 1 (-191.9) TS-2+3-SiAnti-BC B3LYP/6-31G* Geometry O 0 1.385223 1.129608 -0.364594 C 0 1.391968 2.392410 -0.459534 B 0 0.096405 0.229904 -0.385773 C 0 2.680038 3.127579 -0.243423 C 0 -0.900558 0.706726 -1.598587 C 0 0.682114 -1.323975 -0.442459 C 0 -2.347382 0.162766 -1.487106 C 0 -0.347168 0.516266 -3.045853 C 0 -0.134567 -2.279694 -1.359909 C 0 1.070694 -1.922745 0.905136 C 0 -2.544754 -1.302795 -1.882187 C 0 -1.673950 -2.314224 -1.125809 C 0 0.635574 -0.643051 -3.299332 C 0 0.241547 -2.067520 -2.858185 C 0 2.256607 -1.480804 1.524811 C 0 0.331024 -2.904739 1.583893 C 0 0.746353 -3.409744 2.819702 C 0 2.674133 -1.977493 2.758057 C 0 1.917542 -2.948837 3.417816 C 0 -0.530426 0.642761 1.173950 C 0 -0.727493 2.079681 1.237335 C 0 0.251755 2.971649 1.566757 H 0 0.605347 2.890030 -1.027420 H 0 3.248505 3.113815 -1.184998 H 0 2.502625 4.172272 0.023285 H 0 3.284760 2.639771 0.524750 H 0 -1.035294 1.795654 -1.483032 H 0 1.649033 -1.203918 -0.949554 H 0 -3.003052 0.772003 -2.128479 H 0 -2.721359 0.306396 -0.463730 H 0 -1.192932 0.435257 -3.745361 H 0 0.180008 1.432831 -3.349472 H 0 0.203140 -3.297180 -1.118637 H 0 -3.598953 -1.567368 -1.718079 H 0 -2.382797 -1.414948 -2.961639 H 0 -1.885590 -2.217636 -0.053162 H 0 -2.023636 -3.317993 -1.408218

S25

H 0 1.592285 -0.387558 -2.826797 H 0 0.849000 -0.676056 -4.377518 H 0 1.106200 -2.707184 -3.082031 H 0 -0.568970 -2.442703 -3.497437 H 0 2.860748 -0.731232 1.019028 H 0 -0.579987 -3.298538 1.146652 H 0 0.147369 -4.172256 3.312454 H 0 3.598938 -1.613358 3.200317 H 0 2.240768 -3.343674 4.377533 H 0 -1.460663 0.076050 1.274506 H 0 0.192886 0.286072 1.909500 H 0 -1.654861 2.480591 0.824310 H 0 1.139389 2.645569 2.102844 H 0 0.076172 4.044083 1.530457 B3LYP/6-31G* Energy = -879.183586 B3LYP/6-31G* Free Energy = -879.230613 B3LYP/6-31G* Free energy in solution = -879.627091 Number of Imaginary Frequencies = 1 (-179.1) TS-2+3-ReAnti-CB B3LYP/6-31G* Geometry C 0 2.974167 -2.446503 0.264481 C 0 2.993195 -0.892197 0.269745 C 0 1.592468 -3.126205 0.303329 C 0 0.585373 -2.747330 1.406647 B 0 1.695023 -0.184204 -0.419235 C 0 3.354202 -0.325806 1.671188 C 0 0.259308 -0.278809 0.421906 C 0 0.253922 -1.247787 1.660461 C 0 2.578491 -0.891022 2.865800 O 0 2.129013 1.320343 -0.530884 C 0 1.062500 -0.672913 2.853867 C 0 -1.038712 -0.397446 -0.368988 C 0 1.395523 2.245132 -0.991119 C 0 -1.944473 0.679688 -0.394379 C 0 -1.419464 -1.554916 -1.073730 C 0 1.975815 3.620361 -1.136368 C 0 -3.144700 0.626129 -1.105637 C 0 -2.619507 -1.618835 -1.783844 C 0 -3.488449 -0.526489 -1.811752 C 0 1.651611 -0.570190 -2.110474 C 0 0.872100 0.405396 -2.859344 C 0 1.347778 1.613846 -3.276886 H 0 3.595215 -2.829712 1.087265 H 0 3.464645 -2.805756 -0.650909 H 0 3.841370 -0.594254 -0.367111 H 0 1.114380 -2.960541 -0.668488 H 0 1.745500 -4.213898 0.359833 H 0 0.914154 -3.183014 2.360489 H 0 -0.348785 -3.271042 1.163452 H 0 4.421951 -0.519028 1.859253 H 0 3.248276 0.768356 1.656860 H 0 0.186295 0.712296 0.898666 H 0 -0.785889 -1.240524 2.018951 H 0 2.785461 -1.965393 2.957886 H 0 2.978867 -0.441086 3.785843 H 0 0.657761 -1.125259 3.771027 H 0 0.850342 0.403595 2.935715 H 0 0.310455 2.150055 -0.926407 H 0 -1.708893 1.578857 0.173035 H 0 -0.771317 -2.423904 -1.071930

H 0 3.032211 3.570679 -1.410553 H 0 1.422485 4.213913 -1.868134 H 0 1.900269 4.130066 -0.164658 H 0 -3.814438 1.482941 -1.097855 H 0 -2.876404 -2.531052 -2.317230 H 0 -4.421951 -0.577728 -2.365723 H 0 2.698685 -0.589798 -2.429504 H 0 1.227753 -1.573608 -2.192078 H 0 -0.200302 0.231873 -2.938858 H 0 2.416626 1.807632 -3.325989 H 0 0.703949 2.327057 -3.785828 B3LYP/6-31G* Energy = -879.183207 B3LYP/6-31G* Free Energy = -879.229534 B3LYP/6-31G* Free energy in solution = -879.625808 Number of Imaginary Frequencies = 1 (-166.1) TS-2+3-ReAnti-BC B3LYP/6-31G* Geometry C 0 0.764664 -2.414642 2.820251 C 0 0.773544 -0.865051 2.831039 C 0 -0.612961 -3.085693 2.794327 C 0 -1.518723 -2.742828 1.604340 B 0 0.570100 -0.187515 1.361100 C 0 -0.140686 -0.288513 3.954681 C 0 -0.936447 -0.320343 0.660889 C 0 -1.945694 -1.265335 1.411545 C 0 -1.508362 0.276398 3.530746 O 0 0.893021 1.335327 1.600082 C 0 -2.467316 -0.627533 2.733902 C 0 -1.025040 -0.534378 -0.846725 C 0 0.821014 2.220352 0.698593 C 0 -1.666428 0.429337 -1.647598 C 0 -0.523651 -1.669678 -1.511581 C 0 1.242722 3.621964 1.021561 C 0 -1.788284 0.285934 -3.030900 C 0 -0.646790 -1.824631 -2.893463 C 0 -1.276169 -0.845978 -3.664688 C 0 1.936630 -0.592514 0.380142 C 0 2.100204 0.338318 -0.730072 C 0 2.706482 1.554871 -0.631607 H 0 1.285324 -2.776520 3.720352 H 0 1.358673 -2.784470 1.971466 H 0 1.800827 -0.594604 3.122711 H 0 -1.143372 -2.853409 3.726883 H 0 -0.470108 -4.175766 2.807983 H 0 -2.443741 -3.326004 1.724335 H 0 -1.063126 -3.118546 0.680634 H 0 -0.286316 -1.044724 4.740723 H 0 0.392090 0.536896 4.445648 H 0 -1.383255 0.676804 0.806473 H 0 -2.823685 -1.324081 0.752563 H 0 -1.333359 1.192123 2.951859 H 0 -2.040070 0.606720 4.435059 H 0 -2.847977 -1.425507 3.386230 H 0 -3.343903 -0.010864 2.489822 H 0 0.154419 2.065643 -0.152054 H 0 -2.091934 1.310654 -1.169708 H 0 -0.017639 -2.445526 -0.947662 H 0 0.389786 4.138489 1.486100 H 0 2.069946 3.625809 1.735123 H 0 1.516647 4.175766 0.120438

S26

H 0 -2.290527 1.056946 -3.610535 H 0 -0.244751 -2.716217 -3.368866 H 0 -1.368729 -0.966614 -4.740723 H 0 2.796692 -0.571655 1.057083 H 0 1.779358 -1.616943 0.033234 H 0 1.560669 0.118240 -1.650146 H 0 3.343903 1.797333 0.215439 H 0 2.753723 2.231476 -1.481415 B3LYP/6-31G* Energy = -879.183844 B3LYP/6-31G* Free Energy = -879.230445 B3LYP/6-31G* Free energy in solution = -879.626537 Number of Imaginary Frequencies = 1 (-140.6) TS-2+3-SiSyn-CB B3LYP/6-31G* Geometry C 0 0.654663 -2.349792 -2.607697 C 0 0.603607 -0.801239 -2.525558 C 0 -0.686829 -3.085541 -2.506027 C 0 -1.481200 -2.882553 -1.210617 B 0 0.547379 -0.202545 -1.006668 C 0 -0.459503 -0.202667 -3.494766 C 0 -0.751724 -0.676926 -0.067520 C 0 -1.898865 -1.437271 -0.826706 C 0 -1.771240 0.284744 -2.858093 C 0 -1.316620 0.323929 0.930954 C 0 -2.593506 -0.702774 -2.011734 O 0 0.739838 1.331421 -1.194870 C 0 0.859695 2.219986 -0.296677 C 0 1.237839 3.607544 -0.719131 C 0 2.057892 -0.597183 -0.230682 C 0 2.333572 0.303604 0.876114 C 0 2.910675 1.530792 0.738510 C 0 -2.176620 1.382538 0.576462 C 0 -0.999619 0.203629 2.298172 C 0 -1.484009 1.097580 3.254379 C 0 -2.323868 2.145294 2.874115 C 0 -2.671448 2.275940 1.528931 H 0 1.106522 -2.635345 -3.570007 H 0 1.335327 -2.741135 -1.837433 H 0 1.578049 -0.470383 -2.918000 H 0 -1.317108 -2.804962 -3.359924 H 0 -0.502945 -4.162903 -2.625305 H 0 -2.402710 -3.476624 -1.296600 H 0 -0.922882 -3.321167 -0.370193 H 0 -0.683060 -0.918320 -4.299637 H 0 -0.019836 0.668686 -3.998108 H 0 -0.319519 -1.462708 0.568268 H 0 -2.686768 -1.583374 -0.073273 H 0 -1.532349 1.161758 -2.244904 H 0 -2.426987 0.660370 -3.657532 H 0 -3.032608 -1.463562 -2.672302 H 0 -3.453200 -0.143784 -1.618912 H 0 0.370880 2.088928 0.664734 H 0 1.698288 4.162903 0.101532 H 0 0.319855 4.140137 -1.007600 H 0 1.904541 3.585587 -1.584564 H 0 2.825241 -0.530212 -1.008377 H 0 1.955734 -1.637772 0.091019 H 0 1.892563 0.064529 1.844559 H 0 3.453217 1.792923 -0.166702 H 0 3.036072 2.196289 1.588821

H 0 -2.466019 1.517029 -0.459320 H 0 -0.367737 -0.622253 2.619110 H 0 -1.214340 0.965683 4.299637 H 0 -2.709900 2.840714 3.614639 H 0 -3.335709 3.077621 1.214371 B3LYP/6-31G* Energy = -879.183016 B3LYP/6-31G* Free Energy = -879.229443 B3LYP/6-31G* Free energy in solution = -879.625449 Number of Imaginary Frequencies = 1 (-159.3) TS-2+3-SiSyn-BC B3LYP/6-31G* Geometry C 0 2.712021 -2.416000 -0.322586 C 0 2.733917 -0.859222 -0.336868 C 0 1.336319 -3.111893 -0.361633 C 0 0.340652 -2.746002 -1.478241 B 0 1.446976 -0.147842 0.368088 C 0 3.082443 -0.294525 -1.740417 C 0 -0.043747 -0.444107 -0.321884 C 0 -0.020752 -1.244370 -1.681244 C 0 2.277390 -0.845490 -2.920395 O 0 1.869247 1.348541 0.481216 C 0 -1.032288 0.710953 -0.414108 C 0 0.761642 -0.624100 -2.866089 C 0 1.262634 2.302765 1.058319 C 0 1.991943 3.602066 1.228470 C 0 -2.257935 0.639481 0.274002 C 0 -0.810486 1.868896 -1.186859 C 0 -1.761993 2.887268 -1.272629 C 0 -3.210236 1.657745 0.200912 C 0 -2.968781 2.789886 -0.578079 C 0 1.467148 -0.568298 2.062561 C 0 0.709229 0.390991 2.844635 C 0 1.224075 1.556885 3.328232 H 0 3.335617 -2.800690 -1.143188 H 0 3.204636 -2.767487 0.594666 H 0 3.590942 -0.564926 0.289703 H 0 1.504059 -4.197617 -0.409775 H 0 0.836914 -2.946991 0.600891 H 0 0.693466 -3.154480 -2.435150 H 0 -0.586243 -3.292679 -1.254974 H 0 4.144745 -0.500717 -1.946000 H 0 2.992188 0.801285 -1.719086 H 0 -0.525360 -1.148361 0.372437 H 0 -1.066193 -1.244553 -2.022141 H 0 2.481323 -1.919128 -3.025300 H 0 2.654800 -0.388077 -3.846420 H 0 0.335403 -1.055389 -3.784042 H 0 0.548996 0.448639 -2.930481 H 0 0.177429 2.314926 1.093353 H 0 3.057236 3.433029 1.403290 H 0 1.563690 4.197600 2.038254 H 0 1.886276 4.178833 0.298172 H 0 -2.472549 -0.244095 0.872208 H 0 0.130234 1.987396 -1.714493 H 0 -1.555176 3.762833 -1.883789 H 0 -4.144760 1.560898 0.748459 H 0 -3.708572 3.583252 -0.643539 H 0 2.521271 -0.591324 2.357193 H 0 1.050125 -1.576828 2.118576 H 0 -0.373795 0.261810 2.887909

S27

H 0 2.299408 1.699234 3.405136 H 0 0.600937 2.281342 3.846436 B3LYP/6-31G* Energy = -879.182097 B3LYP/6-31G* Free Energy = -879.228845 B3LYP/6-31G* Free energy in solution = -879.624514 Number of Imaginary Frequencies = 1 (-168.8) Product P-2+3-S (Global minimum)

B3LYP/6-31G* Geometry C 0 1.324707 -0.578781 -4.085358 C 0 1.324707 0.962616 -4.085358 C 0 -0.029800 -1.316635 -4.085358 C 0 0.593140 1.647598 -2.886017 C 0 -1.038116 -1.009537 -2.938019 C 0 -2.146973 -0.011673 -3.353638 B 0 0.560700 0.672531 -1.628891 C 0 -0.320908 -0.670242 -1.587967 C 0 -0.793915 2.221558 -3.282806 C 0 -1.726440 1.284866 -4.060104 C 0 -1.286423 -0.766464 -0.409851 O 0 1.407303 1.026550 -0.621674 C 0 1.684189 0.306229 0.590622 C 0 -1.530518 -2.009583 0.198151 C 0 -1.979828 0.347031 0.092392 C 0 1.378220 1.250946 1.767075 C 0 3.141205 -0.144760 0.547607 C 0 -2.424728 -2.138626 1.260864 C 0 -2.878174 0.224518 1.155243 C 0 1.472015 0.580688 3.110046 C 0 -3.104600 -1.019135 1.745056 C 0 2.298798 0.938690 4.093674 H 0 1.888733 -0.924026 -4.962997 H 0 1.910767 -0.922409 -3.219788 H 0 0.915985 1.332000 -5.036300 H 0 2.375946 1.276978 -4.074860 H 0 0.203308 -2.389832 -4.055695 H 0 -0.531754 -1.154129 -5.048965 H 0 1.202011 2.511398 -2.587967 H 0 -1.574265 -1.950912 -2.751114 H 0 -2.751694 0.233261 -2.471161 H 0 -2.824356 -0.547562 -4.033722 H 0 0.409195 -1.484985 -1.438600 H 0 -0.628952 3.114075 -3.904434 H 0 -1.314178 2.586029 -2.383423 H 0 -1.263687 1.037079 -5.024292 H 0 -2.639435 1.841537 -4.313278 H 0 1.028152 -0.568146 0.661209 H 0 -1.006134 -2.889465 -0.169785 H 0 -1.816040 1.327148 -0.349350 H 0 2.054200 2.113663 1.716751 H 0 0.357025 1.628067 1.619888 H 0 3.310455 -0.830719 -0.289413 H 0 3.413345 -0.653946 1.477478 H 0 3.801178 0.720535 0.419373 H 0 -2.588989 -3.114090 1.711914 H 0 -3.399475 1.105133 1.522003 H 0 0.791916 -0.258300 3.268372 H 0 -3.801163 -1.115234 2.573517 H 0 2.310700 0.420563 5.048981 H 0 2.990982 1.771378 3.984146

B3LYP/6-31G* Energy = -879.250631 B3LYP/6-31G* Free Energy = -879.301316 B3LYP/6-31G* Free energy in solution = -879.691106 Number of Imaginary Frequencies = 0 Product P-2+3-S (from IRC of TS-2+3-ReSyn-CB)

B3LYP/6-31G* Geometry O 0 0.129486 0.755966 0.426620 C 0 0.129486 2.184402 0.426620 B 0 -0.932709 -0.094543 0.426620 C 0 1.110413 2.646866 1.501297 C 0 -2.455124 0.362274 0.532349 C 0 -0.551590 -1.646500 0.293503 C 0 0.533325 2.672653 -0.978226 C 0 -3.377106 -0.281494 -0.545380 C 0 -2.949112 0.127502 1.995178 C 0 -1.643097 -2.647202 0.794495 C 0 0.868515 -1.966614 0.737366 C 0 -0.480469 2.349670 -2.040924 C 0 -3.857422 -1.717300 -0.293686 C 0 -2.784409 -2.812134 -0.240677 C 0 -2.190414 -0.960251 2.781464 C 0 -2.205536 -2.397980 2.229965 C 0 1.192139 -2.362793 2.044342 C 0 1.925186 -1.855942 -0.181534 C 0 -0.281677 1.514908 -3.062576 C 0 3.243362 -2.125656 0.182556 C 0 2.510605 -2.637466 2.415054 C 0 3.544815 -2.520386 1.487503 H 0 -0.873260 2.562424 0.664032 H 0 2.114365 2.263245 1.290924 H 0 0.804352 2.274384 2.484100 H 0 1.152481 3.740952 1.542419 H 0 -2.523621 1.441727 0.345718 H 0 -0.541748 -1.769165 -0.804398 H 0 1.503189 2.226151 -1.229156 H 0 0.677017 3.761688 -0.924927 H 0 -4.275497 0.346329 -0.637238 H 0 -2.878891 -0.229263 -1.524658 H 0 -4.026276 -0.089279 2.004303 H 0 -2.831741 1.064026 2.555984 H 0 -1.152771 -3.629562 0.826630 H 0 -1.448730 2.844116 -1.942841 H 0 -4.570389 -1.980408 -1.087402 H 0 -4.441330 -1.740509 0.635498 H 0 -2.336929 -2.932449 -1.237976 H 0 -3.295410 -3.761688 -0.026642 H 0 -2.594437 -0.991257 3.802979 H 0 -1.143845 -0.638123 2.896011 H 0 -1.641754 -3.014328 2.941635 H 0 -3.232590 -2.786484 2.274353 H 0 0.410568 -2.463669 2.789902 H 0 1.705383 -1.552994 -1.203125 H 0 -1.053268 1.320877 -3.802979 H 0 0.667633 1.001709 -3.201813 H 0 4.035797 -2.033585 -0.556519 H 0 2.725967 -2.945786 3.435440 H 0 4.570374 -2.736954 1.774948 B3LYP/6-31G* Energy = -879.248022 B3LYP/6-31G* Free Energy = -879.29952 B3LYP/6-31G* Free energy in solution = -879.68812

S28

Number of Imaginary Frequencies = 0 Product P-2+3-R (Global minimum)

B3LYP/6-31G* Geometry C 0 1.007675 -0.558777 -2.925156 C 0 1.007675 0.982956 -2.925156 C 0 -0.346298 -1.298096 -2.925156 C 0 0.264969 1.671143 -1.734268 C 0 -1.356018 -0.990646 -1.779663 C 0 -2.467392 0.000443 -2.203705 B 0 0.225723 0.704437 -0.468506 C 0 -0.642914 -0.646027 -0.429428 C 0 -1.121231 2.237732 -2.146759 C 0 -2.047943 1.290848 -2.919083 C 0 -1.609207 -0.757980 0.745972 O 0 1.059372 1.079254 0.543640 C 0 1.333649 0.380951 1.769440 C 0 -2.339478 0.339569 1.230530 C 0 -1.824219 -2.002029 1.362457 C 0 2.844360 0.083939 1.824524 C 0 0.884094 1.259964 2.933014 C 0 -3.247635 0.200668 2.282867 C 0 -2.727432 -2.147263 2.415375 C 0 3.338882 -0.778625 0.695908 C 0 -3.445770 -1.044052 2.880524 C 0 3.807861 -2.020294 0.830750 H 0 1.571503 -0.903183 -3.803253 H 0 1.592500 -0.904007 -2.059906 H 0 0.608429 1.352448 -3.880005 H 0 2.059036 1.297668 -2.905777 H 0 -0.111053 -2.370712 -2.893372 H 0 -0.847244 -1.138474 -3.889679 H 0 0.867706 2.539764 -1.437454 H 0 -1.889206 -1.933167 -1.590561 H 0 -3.076950 0.248795 -1.325638 H 0 -3.140350 -0.542800 -2.882385 H 0 0.097992 -1.450700 -0.281189 H 0 -0.953445 3.122986 -2.777893 H 0 -1.646622 2.612198 -1.254562 H 0 -2.960907 1.843536 -3.181305 H 0 -1.580811 1.035355 -3.879028 H 0 0.784225 -0.565964 1.789307 H 0 -2.196884 1.319946 0.782089 H 0 -1.270889 -2.869431 1.007858 H 0 3.374054 1.047424 1.815018 H 0 3.061905 -0.398514 2.785690 H 0 1.102722 0.772644 3.889694 H 0 1.404434 2.223877 2.905472 H 0 -0.192932 1.443130 2.881058 H 0 -3.798996 1.068893 2.635010 H 0 -2.869034 -3.122971 2.873520 H 0 3.298889 -0.330673 -0.296463 H 0 -4.149979 -1.153427 3.700821 H 0 4.149994 -2.599487 -0.022858 H 0 3.874725 -2.504807 1.803268 B3LYP/6-31G* Energy = -879.250680 B3LYP/6-31G* Free Energy = -879.300836 B3LYP/6-31G* Free energy in solution = -879.691088 Number of Imaginary Frequencies = 0

Product P-2+3-R (from IRC of TS-2+3-SiAnti-CB)

B3LYP/6-31G* Geometry O 0 0.213318 0.774780 -1.076874 C 0 0.213318 2.203537 -1.076874 B 0 -0.838135 -0.087769 -1.076874 C 0 0.896957 2.678879 -2.356949 C 0 -2.364563 0.353958 -1.179428 C 0 -0.415726 -1.638900 -1.077835 C 0 0.952087 2.674484 0.190369 C 0 -3.098953 0.097794 0.172531 C 0 -3.082321 -0.285965 -2.407654 C 0 -1.570282 -2.652603 -0.802948 C 0 0.884811 -1.905777 -0.329727 C 0 0.198517 2.395157 1.461929 C 0 -2.487015 -0.998200 1.065704 C 0 -2.399887 -2.427414 0.500580 C 0 -3.566833 -1.734589 -2.263412 C 0 -2.494766 -2.808624 -2.038666 C 0 2.112076 -1.691193 -0.980667 C 0 0.933426 -2.348206 1.001100 C 0 0.565033 1.511261 2.391449 C 0 2.151291 -2.562424 1.652664 C 0 3.329529 -1.901215 -0.336182 C 0 3.357040 -2.338745 0.989914 H 0 -0.817032 2.580566 -1.053192 H 0 0.357666 2.316055 -3.238297 H 0 0.927094 3.773346 -2.397446 H 0 1.923645 2.299545 -2.404343 H 0 -2.416168 1.435104 -1.364761 H 0 -0.160736 -1.790482 -2.142303 H 0 1.932114 2.183395 0.212936 H 0 1.126236 3.756088 0.095154 H 0 -4.162491 -0.113663 -0.006516 H 0 -3.077103 1.027191 0.756195 H 0 -3.963821 0.329163 -2.639877 H 0 -2.430313 -0.210281 -3.291428 H 0 -1.085968 -3.632538 -0.691864 H 0 -0.719406 2.968567 1.607193 H 0 -3.067734 -1.043411 1.997818 H 0 -1.480652 -0.671844 1.366852 H 0 -1.987976 -3.059769 1.297043 H 0 -3.416565 -2.810974 0.338074 H 0 -4.304153 -1.784744 -1.452209 H 0 -4.123169 -1.997238 -3.173981 H 0 -1.868011 -2.891281 -2.938721 H 0 -3.013565 -3.773361 -1.946915 H 0 2.107803 -1.351791 -2.013733 H 0 0.014618 -2.533707 1.545654 H 0 -0.023590 1.352524 3.291443 H 0 1.465668 0.910919 2.285522 H 0 2.151596 -2.909561 2.683289 H 0 4.259369 -1.729004 -0.873200 H 0 4.304138 -2.508591 1.495331 B3LYP/6-31G* Energy = -879.248004 B3LYP/6-31G* Free Energy = -879.29985 B3LYP/6-31G* Free energy in solution = -879.689049 Number of Imaginary Frequencies = 0

S29

Allylboration Reaction between 1 and 4 Complex (1-4)-ReSyn-CB B3LYP/6-31G* Geometry O 0 3.184738 2.366180 -1.592834 C 0 4.091461 1.815292 -2.205276 C 0 5.374191 2.536819 -2.482895 C 0 3.927719 0.387756 -2.696625 C 0 6.436386 1.940918 -3.180466 C 0 5.513138 3.857773 -2.026276 C 0 7.613037 2.651108 -3.416245 C 0 6.687225 4.565796 -2.261795 C 0 7.740112 3.963394 -2.957428 B 0 -0.498276 2.267014 -1.298233 C 0 -0.437363 1.522690 -2.702454 C 0 -1.212128 3.663651 -1.117325 C 0 0.053711 1.502930 -0.001617 C 0 -1.880814 0.978897 -2.969345 C 0 0.136032 2.300156 -3.919495 C 0 -2.028503 4.176544 -2.343094 Si 0 -0.234665 5.048630 -0.179550 C 0 0.000000 0.000000 0.000000 C 0 -2.882751 1.980438 -3.557617 C 0 -3.196930 3.222794 -2.712906 C 0 0.160522 3.831955 -3.805222 C 0 -1.166718 4.576813 -3.575180 C 0 -0.052765 4.586166 1.654556 C 0 -1.258224 6.649323 -0.242386 C 0 1.500931 5.447906 -0.832275 C 0 1.050888 -0.824860 0.000000 H 0 2.950165 0.016159 -2.385361 H 0 4.710648 -0.262970 -2.289307 H 0 4.002335 0.341476 -3.789856 H 0 6.350189 0.921448 -3.543000 H 0 4.685242 4.309800 -1.490265 H 0 8.429443 2.180832 -3.957245 H 0 6.784958 5.587433 -1.905075 H 0 8.657440 4.516388 -3.141266 H 0 0.179367 0.624130 -2.574890 H 0 -1.953278 3.461884 -0.317841 H 0 -0.435043 1.881332 0.907349 H 0 1.110580 1.815170 0.062271 H 0 -1.801239 0.132751 -3.667160 H 0 -2.299911 0.553665 -2.043808 H 0 -0.385117 1.999680 -4.840073 H 0 1.178329 1.985947 -4.059891 H 0 -2.538528 5.096786 -2.028152 H 0 -0.999283 -0.441315 0.006027 H 0 -3.827042 1.449387 -3.743530 H 0 -2.531555 2.300156 -4.546936 H 0 -3.696411 2.912582 -1.782486 H 0 -3.941833 3.811142 -3.268478 H 0 0.614059 4.239380 -4.720535 H 0 0.854660 4.090271 -2.998520 H 0 -0.912643 5.642792 -3.487823 H 0 -1.789352 4.505356 -4.478287 H 0 0.657349 3.768051 1.812912 H 0 -1.009140 4.290146 2.102768 H 0 0.316757 5.453873 2.216064 H 0 -1.346619 7.051453 -1.258240 H 0 -0.777985 7.420380 0.373352 H 0 -2.273315 6.503204 0.146561

H 0 1.995346 6.131577 -0.129196 H 0 1.473572 5.948303 -1.806656 H 0 2.126633 4.553635 -0.928589 H 0 2.070435 -0.444321 0.009644 H 0 0.932510 -1.905624 0.000000 B3LYP/6-31G* Energy = -1287.773459 B3LYP/6-31G* Free Energy = -1287.838645 B3LYP/6-31G* Free energy in solution = -1288.303629 Number of Imaginary Frequencies = 0 HOMO = -6.17 LUMO = -1.67 Complex (1-4)-ReSyn-BC B3LYP/6-31G* Geometry O 0 0.533933 0.790239 0.655208 C 0 0.558032 1.998546 0.856100 C 0 1.736486 2.819308 0.433963 C 0 -0.612918 2.682866 1.539791 C 0 2.814574 2.169681 -0.189404 C 0 1.801176 4.206192 0.639171 C 0 3.930691 2.891211 -0.600306 C 0 2.920541 4.928865 0.227709 C 0 3.985534 4.273005 -0.392691 H 0 -1.380235 1.937380 1.753949 H 0 -1.038155 3.466124 0.901259 H 0 -0.297402 3.159669 2.475611 H 0 2.753179 1.097093 -0.340543 H 0 0.979750 4.728366 1.119928 H 0 4.759230 2.379979 -1.082684 H 0 2.961142 6.002290 0.390456 H 0 4.857304 4.836908 -0.713814 B 0 -1.136470 -2.484094 -0.373095 C 0 -2.380007 -1.516406 -0.578397 C 0 -1.221394 -3.742975 0.563975 C 0 0.202421 -2.189200 -1.205481 C 0 -3.342354 -2.230084 -1.587934 C 0 -3.106800 -1.030758 0.703917 C 0 -2.658664 -4.224387 0.933397 Si 0 -0.009523 -3.637465 2.069419 C 0 0.001828 -1.735802 -2.626499 C 0 -3.260542 -3.771398 -1.622550 C 0 -3.521573 -4.562410 -0.324029 C 0 -4.050788 -2.026742 1.388169 C 0 -3.414601 -3.311541 1.930719 C 0 1.766280 -3.951629 1.474358 C 0 -0.427657 -5.011421 3.314592 C 0 -0.020237 -1.967493 2.970680 C 0 0.147809 -0.488227 -3.082029 H 0 -2.023634 -0.607430 -1.079967 H 0 -0.728478 -4.562299 0.007326 H 0 0.882027 -3.052657 -1.189435 H 0 0.700722 -1.378422 -0.647500 H 0 -4.379504 -1.917432 -1.402308 H 0 -3.100269 -1.879000 -2.598342 H 0 -3.706858 -0.146851 0.437456 H 0 -2.361398 -0.673554 1.428541 H 0 -2.546412 -5.176822 1.469644 H 0 -0.305091 -2.510973 -3.332482 H 0 -2.266673 -4.054471 -2.002081 H 0 -3.966179 -4.137640 -2.381551 H 0 -3.364719 -5.620923 -0.573184

S30

H 0 -4.584397 -4.481593 -0.055714 H 0 -4.857304 -2.292090 0.692502 H 0 -4.548063 -1.514915 2.224470 H 0 -4.219759 -3.912057 2.379104 H 0 -2.743716 -3.054301 2.760183 H 0 2.139175 -3.146104 0.833110 H 0 1.850294 -4.890516 0.913454 H 0 2.440770 -4.023494 2.337192 H 0 -0.407495 -6.002290 2.844495 H 0 -1.413511 -4.881690 3.774438 H 0 0.314290 -5.017190 4.123279 H 0 0.750008 -1.966523 3.753245 H 0 -0.979431 -1.756896 3.456886 H 0 0.198117 -1.135365 2.291161 H 0 0.457315 0.322977 -2.425977 H 0 -0.034507 -0.233705 -4.123279 B3LYP/6-31G* Energy = -1287.775887 B3LYP/6-31G* Free Energy = -1287.844196 B3LYP/6-31G* Free energy in solution = -1288.303961 Number of Imaginary Frequencies = 0 HOMO = -6.07 LUMO = -1.69 Complex (1-4)-SiAnti-CB B3LYP/6-31G* Geometry O 0 -2.039398 2.560425 -2.515060 C 0 -2.985397 2.153351 -3.178300 C 0 -3.861526 3.112244 -3.924561 C 0 -3.280975 0.666046 -3.257233 C 0 -4.941788 2.689346 -4.714188 C 0 -3.583633 4.485275 -3.826675 C 0 -4.367294 5.414368 -4.503052 C 0 -5.726822 3.620911 -5.393051 C 0 -5.441010 4.983368 -5.288452 B 0 1.286774 2.012878 -1.200073 C 0 2.117050 1.002762 -2.112610 C 0 1.236923 3.561035 -1.503296 C 0 0.389343 1.451294 0.003860 C 0 1.353668 0.900528 -3.476730 C 0 3.634598 1.291428 -2.294357 C 0 1.935883 4.033295 -2.815964 Si 0 1.488663 4.745316 0.003357 C 0 0.000000 0.000000 0.000000 C 0 1.641113 2.009140 -4.496063 C 0 1.265289 3.437744 -4.083023 C 0 4.096115 2.726990 -2.000977 C 0 3.484131 3.876755 -2.820908 C 0 2.928482 4.311737 1.168274 C 0 -0.089783 4.802094 1.059800 C 0 1.784714 6.515945 -0.621750 C 0 -1.252991 -0.463379 0.000015 H 0 -3.187119 0.305100 -4.288757 H 0 -4.303345 0.446915 -2.927368 H 0 -2.571838 0.132996 -2.621582 H 0 -5.173706 1.632767 -4.803986 H 0 -2.745926 4.797989 -3.212204 H 0 -4.144363 6.474625 -4.421051 H 0 -6.560486 3.283691 -6.002762 H 0 -6.053421 5.708618 -5.817551 H 0 2.040665 -0.003036 -1.681732 H 0 0.153473 3.728729 -1.655472

H 0 1.007202 1.639389 0.904800 H 0 -0.507324 2.069077 0.132400 H 0 0.270828 0.853531 -3.290909 H 0 1.620239 -0.060669 -3.940109 H 0 4.191650 0.638000 -1.609390 H 0 3.957642 0.993195 -3.301895 H 0 1.749298 5.111526 -2.909225 H 0 0.816696 -0.723267 0.005463 H 0 1.096771 1.770020 -5.420914 H 0 2.703186 1.980179 -4.772308 H 0 0.175659 3.500717 -3.955765 H 0 1.512253 4.095490 -4.929764 H 0 3.916855 2.924210 -0.937469 H 0 5.187744 2.772018 -2.125244 H 0 3.829346 3.806900 -3.862152 H 0 3.928909 4.804367 -2.433960 H 0 2.873306 3.282730 1.543533 H 0 2.900162 4.976639 2.041260 H 0 3.907455 4.440750 0.693909 H 0 -0.270569 3.868378 1.602158 H 0 -0.976837 5.006485 0.447998 H 0 -0.009933 5.604568 1.804337 H 0 2.720642 6.615280 -1.183380 H 0 1.840164 7.204025 0.231461 H 0 0.970566 6.862823 -1.269669 H 0 -2.107437 0.210678 0.007355 H 0 -1.470642 -1.528580 0.000000 B3LYP/6-31G* Energy = -1287.773083 B3LYP/6-31G* Free Energy = -1287.840686 B3LYP/6-31G* Free energy in solution = -1288.300975 Number of Imaginary Frequencies = 0 HOMO = -6.16 LUMO = -1.65 Complex (1-4)-SiAnti-BC B3LYP/6-31G* Geometry O 0 1.187531 0.300949 -0.000031 C 0 0.000000 0.000000 0.000000 C 0 -1.055878 1.062180 0.000000 C 0 -0.420822 -1.459015 -0.000229 C 0 -0.651306 2.406693 0.031479 C 0 -2.426682 0.762787 -0.032013 C 0 -3.373016 1.787048 -0.035202 C 0 -1.595596 3.428162 0.029877 C 0 -2.959137 3.119965 -0.004211 B 0 4.480927 -1.516235 -2.261520 C 0 5.078491 -2.789490 -3.011810 C 0 3.462723 -0.553528 -2.963287 C 0 4.865158 -1.287598 -0.723038 C 0 3.966049 -3.892014 -3.057861 C 0 5.700897 -2.513611 -4.408539 C 0 2.805847 -1.072205 -4.277496 Si 0 4.115265 1.268021 -3.068573 C 0 4.534378 -2.493927 0.119232 C 0 2.509079 -3.387802 -2.995712 C 0 2.012741 -2.401093 -4.071442 C 0 4.724426 -2.338486 -5.577835 C 0 3.761185 -1.148773 -5.494293 C 0 4.022583 2.104492 -1.367874 C 0 2.998306 2.265518 -4.238510 C 0 5.914139 1.405869 -3.670044

S31

C 0 3.541321 -2.552231 1.012360 H 0 0.473419 -2.084320 0.013565 H 0 -1.013840 -1.695404 -0.892014 H 0 -1.040970 -1.690720 0.873840 H 0 0.411072 2.625381 0.057785 H 0 -2.761703 -0.269500 -0.056274 H 0 -4.431824 1.545120 -0.061691 H 0 -1.272766 4.465332 0.055069 H 0 -3.697037 3.917770 -0.006149 H 0 5.899857 -3.200500 -2.406311 H 0 2.664017 -0.392853 -2.215149 H 0 5.954681 -1.112076 -0.674515 H 0 4.372604 -0.409134 -0.295929 H 0 4.100784 -4.554810 -2.194214 H 0 4.105911 -4.527390 -3.943573 H 0 6.358719 -1.633789 -4.351974 H 0 6.360733 -3.358200 -4.657761 H 0 2.052246 -0.329010 -4.571442 H 0 5.147415 -3.381668 -0.042892 H 0 1.844116 -4.262970 -3.016830 H 0 2.352737 -2.933670 -2.007141 H 0 1.934570 -2.920197 -5.037445 H 0 0.980057 -2.143784 -3.797272 H 0 5.310500 -2.236740 -6.502090 H 0 4.144943 -3.262009 -5.704330 H 0 3.138168 -1.168762 -6.400528 H 0 4.339539 -0.217880 -5.555664 H 0 4.835892 1.789841 -0.705093 H 0 3.077026 1.885071 -0.859512 H 0 4.102661 3.192947 -1.486862 H 0 3.017670 1.897964 -5.270218 H 0 3.322113 3.313965 -4.256012 H 0 1.955338 2.250168 -3.899063 H 0 6.598068 0.849991 -3.016235 H 0 6.235046 2.455429 -3.655900 H 0 6.056091 1.032654 -4.690079 H 0 2.902191 -1.692429 1.202835 H 0 3.338272 -3.456543 1.580872 B3LYP/6-31G* Energy = -1287.775597 B3LYP/6-31G* Free Energy = -1287.840800 B3LYP/6-31G* Free energy in solution = -1288.301247 Number of Imaginary Frequencies = 0 HOMO = -6.10 LUMO = -1.68 TS-1+4-ReSyn-CB B3LYP/6-31G* Geometry O 0 -0.269714 0.158264 -0.110062 C 0 -0.272522 1.456924 -0.082886 B 0 -1.389053 -0.903351 -0.065735 C 0 1.003265 2.108215 -0.539322 C 0 -1.042389 2.220154 0.981735 C 0 -2.380081 -0.800735 1.236893 C 0 -0.785858 -2.407745 -0.368011 C 0 1.104630 3.501389 -0.705185 C 0 2.145172 1.327103 -0.773422 C 0 -3.570435 -1.804535 1.236084 C 0 -1.593781 -0.837906 2.583649 C 0 -0.869110 -3.467957 0.793274 Si 0 0.858612 -2.622528 -1.322647 C 0 2.305008 4.088791 -1.097092

C 0 3.348465 1.916687 -1.158020 C 0 -3.306549 -3.221527 1.757385 C 0 -2.294128 -4.053726 0.968857 C 0 -0.245850 -1.581329 2.566574 C 0 -0.236664 -3.063721 2.157928 C 0 1.004654 -1.496384 -2.851273 C 0 0.927261 -4.389557 -2.037582 C 0 2.409637 -2.447067 -0.228775 C 0 3.434600 3.299042 -1.323349 H 0 -2.037506 1.816879 1.143875 H 0 -1.128494 3.278885 0.735123 H 0 -0.479477 2.145294 1.921783 H 0 -2.887772 0.173584 1.205353 H 0 -1.479385 -2.815948 -1.125931 H 0 0.238892 4.137161 -0.550812 H 0 2.084885 0.256485 -0.638840 H 0 -4.371704 -1.380600 1.860504 H 0 -3.998000 -1.875412 0.225220 H 0 -2.228638 -1.246307 3.383209 H 0 -1.376312 0.192337 2.895645 H 0 -0.287140 -4.341766 0.465820 H 0 2.357224 5.166290 -1.227234 H 0 4.220886 1.290726 -1.324310 H 0 -4.262222 -3.765060 1.772690 H 0 -2.989304 -3.167969 2.806732 H 0 -2.702057 -4.275650 -0.028305 H 0 -2.198730 -5.025803 1.476089 H 0 0.197311 -1.511795 3.570831 H 0 0.438339 -1.037903 1.905136 H 0 0.815536 -3.376572 2.161682 H 0 -0.715042 -3.660843 2.947754 H 0 0.959763 -0.430161 -2.614807 H 0 0.205704 -1.715851 -3.570816 H 0 1.956329 -1.683731 -3.365570 H 0 0.916031 -5.166275 -1.264282 H 0 1.845505 -4.527893 -2.623108 H 0 0.080673 -4.581879 -2.708908 H 0 3.319397 -2.424225 -0.842484 H 0 2.496674 -3.310013 0.442764 H 0 2.406830 -1.551895 0.401764 H 0 4.371704 3.758652 -1.625259 C 0 -2.278137 -0.429565 -1.568665 C 0 -2.494583 0.982071 -1.538605 C 0 -1.523285 1.897842 -1.879059 H 0 -3.185593 -1.032990 -1.515152 H 0 -1.626373 -0.759659 -2.378311 H 0 -3.378265 1.350159 -1.014847 H 0 -0.722321 1.607910 -2.551880 H 0 -1.717545 2.964432 -1.808884 B3LYP/6-31G* Energy = -1287.748317 B3LYP/6-31G* Free Energy = -1287.802797 B3LYP/6-31G* Free energy in solution = -1288.287117 Number of Imaginary Frequencies = 1 (-326.1)

TS-1+4-ReSyn-BC B3LYP/6-31G* Geometry O 0 -0.236237 0.154449 -0.318451 C 0 -0.242538 1.454147 -0.302719 B 0 -1.348267 -0.912750 -0.283173 C 0 1.031525 2.104233 -0.765884 C 0 -1.016342 2.233810 0.748932

S32

C 0 -2.330856 -0.800552 1.027893 C 0 -0.722260 -2.404312 -0.597076 C 0 2.171646 1.321609 -1.002472 C 0 1.133423 3.496857 -0.936737 C 0 -3.517975 -1.812866 1.100449 C 0 -1.544540 -0.763382 2.366700 C 0 -0.737259 -3.412018 0.606354 Si 0 0.899979 -2.616104 -1.587967 C 0 3.374100 1.908447 -1.393387 C 0 2.332932 4.081787 -1.334976 C 0 -3.362167 -3.201050 0.451157 C 0 -2.139450 -4.056015 0.823181 C 0 -1.018875 -2.104141 2.885056 C 0 -0.108170 -2.871796 1.919739 C 0 1.021042 -1.479019 -3.110519 C 0 0.926590 -4.381042 -2.310730 C 0 2.485900 -2.466934 -0.541702 C 0 3.460968 3.290359 -1.562851 H 0 -2.003967 1.821243 0.930344 H 0 -1.120789 3.283478 0.472244 H 0 -0.448334 2.195236 1.687958 H 0 -2.833633 0.175125 0.977936 H 0 -1.419113 -2.841293 -1.334030 H 0 2.108963 0.251556 -0.865616 H 0 0.269180 4.134247 -0.781158 H 0 -3.804398 -1.942505 2.154953 H 0 -4.397385 -1.353607 0.626343 H 0 -2.191254 -0.332779 3.147888 H 0 -0.691422 -0.078949 2.269577 H 0 -0.088181 -4.257050 0.334457 H 0 4.245117 1.281021 -1.561508 H 0 2.385666 5.158829 -1.468674 H 0 -3.373596 -3.078873 -0.639038 H 0 -4.265869 -3.783508 0.682327 H 0 -2.196396 -4.963486 0.205826 H 0 -2.229752 -4.406982 1.860443 H 0 -1.862045 -2.742508 3.177505 H 0 -0.459045 -1.919968 3.813187 H 0 0.296356 -3.733200 2.471100 H 0 0.756363 -2.242966 1.669556 H 0 0.993515 -0.414566 -2.862686 H 0 0.203125 -1.682480 -3.813171 H 0 1.958344 -1.670990 -3.648926 H 0 0.077759 -4.546982 -2.986282 H 0 0.888794 -5.158813 -1.539108 H 0 1.843048 -4.544600 -2.892380 H 0 3.374084 -2.507431 -1.185562 H 0 2.558319 -3.306061 0.160600 H 0 2.544922 -1.548904 0.052124 H 0 4.397400 3.748184 -1.869492 C 0 -2.262024 -0.445847 -1.773773 C 0 -2.467163 0.967606 -1.747879 C 0 -1.493118 1.874725 -2.103439 H 0 -3.173386 -1.040741 -1.693481 H 0 -1.630569 -0.785600 -2.595444 H 0 -3.341965 1.345856 -1.216568 H 0 -0.697998 1.574066 -2.778580 H 0 -1.680527 2.942947 -2.041321 B3LYP/6-31G* Energy = -1287.748085 B3LYP/6-31G* Free Energy = -1287.802769 B3LYP/6-31G* Free energy in solution = -1288.28654 Number of Imaginary Frequencies = 1 (-325.6)

TS-1+4-SiAnti-CB B3LYP/6-31G* Geometry O 0 -0.214325 0.366318 -0.020493 C 0 -0.201263 1.663681 -0.070847 B 0 -1.282532 -0.724700 -0.100357 C 0 1.030563 2.283173 0.525925 C 0 -0.840500 2.399979 -1.236969 C 0 -2.198730 -0.690613 -1.455963 C 0 -0.468384 -2.132278 0.218277 C 0 1.282425 3.663635 0.451340 C 0 1.974472 1.465149 1.169525 C 0 -1.365600 -0.742386 -2.766632 C 0 -3.376663 -1.712692 -1.480500 C 0 -0.592117 -3.267410 -0.856735 Si 0 -0.374191 -2.864136 1.990143 C 0 3.132355 2.010193 1.718414 C 0 2.441010 4.207550 1.003723 C 0 -0.892639 -2.124481 -3.224838 C 0 0.000931 -2.884323 -2.241150 C 0 -3.213074 -3.017975 -0.680954 C 0 -2.000031 -3.915100 -0.971588 C 0 -2.011459 -3.376556 2.817764 C 0 0.531784 -1.664078 3.165390 C 0 0.708389 -4.432800 1.979630 C 0 3.371460 3.383926 1.638992 H 0 -0.155304 2.352676 -2.093765 H 0 -1.017197 3.452118 -1.008789 H 0 -1.783539 1.946655 -1.529404 H 0 -2.695755 0.289398 -1.486023 H 0 0.587158 -1.813995 0.133255 H 0 0.574081 4.327774 -0.032150 H 0 1.790176 0.399124 1.223816 H 0 -0.485947 -0.091064 -2.667648 H 0 -1.968307 -0.314346 -3.583389 H 0 -4.275040 -1.220551 -1.080627 H 0 -3.630737 -1.953812 -2.523056 H 0 0.070786 -4.077164 -0.524689 H 0 3.852219 1.359070 2.206970 H 0 2.615860 5.277847 0.935608 H 0 -0.341782 -2.005463 -4.168961 H 0 -1.763641 -2.744080 -3.474838 H 0 0.927307 -2.314224 -2.076385 H 0 0.307892 -3.818100 -2.735748 H 0 -3.197266 -2.771072 0.385818 H 0 -4.122284 -3.619843 -0.825607 H 0 -2.105042 -4.372925 -1.965347 H 0 -2.057632 -4.754349 -0.263596 H 0 -2.713150 -2.547333 2.956329 H 0 -1.799805 -3.795273 3.810410 H 0 -2.527039 -4.154724 2.242889 H 0 0.054733 -0.683578 3.271179 H 0 1.558731 -1.490753 2.819153 H 0 0.599991 -2.103363 4.168945 H 0 0.223465 -5.277847 1.477203 H 0 0.920853 -4.746017 3.009949 H 0 1.672180 -4.262924 1.483658 H 0 4.275040 3.808807 2.067535 C 0 -2.338043 -0.174271 1.291306 C 0 -2.549469 1.229187 1.151047 C 0 -1.616455 2.168274 1.541672 H 0 -3.232941 -0.785217 1.173584 H 0 -1.781982 -0.438217 2.188782

S33

H 0 -3.371292 1.562897 0.516052 H 0 -0.899475 1.919495 2.317947 H 0 -1.802826 3.229095 1.398834 B3LYP/6-31G* Energy = -1287.747593 B3LYP/6-31G* Free Energy = -1287.802447 B3LYP/6-31G* Free energy in solution = -1288.28552 Number of Imaginary Frequencies = 1 (-354.3) TS-1+4-SiAnti-BC B3LYP/6-31G* Geometry O 0 -0.277344 0.363403 -0.217651 C 0 -0.259384 1.659760 -0.265656 B 0 -1.356506 -0.720520 -0.313049 C 0 0.970688 2.275497 0.338700 C 0 -0.882996 2.397934 -1.438156 C 0 -2.278229 -0.663147 -1.670517 C 0 -0.562729 -2.142731 -0.006027 C 0 1.956833 1.445435 0.897415 C 0 1.181717 3.664932 0.348953 C 0 -1.450256 -0.761032 -2.987976 C 0 -3.490234 -1.635269 -1.693741 C 0 -0.781631 -3.296494 -1.042374 Si 0 -0.430923 -2.838043 1.779785 C 0 2.341156 4.205750 0.901550 C 0 3.117249 1.987732 1.444748 C 0 -0.123276 -1.536560 -2.918945 C 0 -0.159927 -2.998764 -2.441696 C 0 -3.207443 -3.095078 -2.057159 C 0 -2.233505 -3.834122 -1.135590 C 0 0.532974 -1.629639 2.898361 C 0 0.619797 -4.428711 1.776337 C 0 -2.054092 -3.295013 2.668900 C 0 3.315109 3.369904 1.450485 H 0 -1.844452 1.975174 -1.717010 H 0 -0.203735 2.309128 -2.296677 H 0 -1.017303 3.460022 -1.229050 H 0 -2.759995 0.325348 -1.689621 H 0 0.498322 -1.857300 -0.133286 H 0 1.804489 0.373184 0.885696 H 0 0.437332 4.337997 -0.063354 H 0 -1.197617 0.254242 -3.323059 H 0 -2.076370 -1.177582 -3.790878 H 0 -4.009995 -1.610214 -0.725281 H 0 -4.220184 -1.253616 -2.424271 H 0 -0.208664 -4.157806 -0.675766 H 0 2.482941 5.283081 0.901917 H 0 3.870972 1.327438 1.865143 H 0 0.334808 -1.522476 -3.918716 H 0 0.566360 -0.979340 -2.273285 H 0 -0.658951 -3.621979 -3.197510 H 0 0.883591 -3.343597 -2.426987 H 0 -4.162048 -3.640671 -2.059631 H 0 -2.840866 -3.148880 -3.090363 H 0 -2.180267 -4.875687 -1.485550 H 0 -2.664078 -3.880569 -0.126282 H 0 0.098800 -0.626297 2.965164 H 0 1.562592 -1.513824 2.536438 H 0 0.592545 -2.029678 3.918716 H 0 0.094009 -5.283066 1.334854 H 0 0.881439 -4.705093 2.805908 H 0 1.558731 -4.297623 1.223862

H 0 -2.738724 -2.450211 2.796280 H 0 -1.819672 -3.680450 3.669983 H 0 -2.599533 -4.085861 2.140732 H 0 4.220200 3.792450 1.878159 C 0 -2.384354 -0.182785 1.091461 C 0 -2.621567 1.216888 0.949982 C 0 -1.700653 2.169830 1.334702 H 0 -3.267900 -0.815247 1.001572 H 0 -1.801361 -0.430664 1.975937 H 0 -3.452545 1.535522 0.319321 H 0 -0.981018 1.935654 2.112854 H 0 -1.899353 3.227203 1.182755 B3LYP/6-31G* Energy = -1287.747898 B3LYP/6-31G* Free Energy = -1287.80334 B3LYP/6-31G* Free energy in solution = -1288.284954 Number of Imaginary Frequencies = 1 (-348.5) TS-1+4-ReAnti-CB B3LYP/6-31G* Geometry C 0 -1.827316 -1.511322 -2.701660 C 0 -2.064117 -0.001785 -2.424393 C 0 -2.862549 -2.480469 -2.132431 C 0 -3.072510 -2.401474 -0.618622 B 0 -1.605698 0.476257 -0.916809 C 0 -3.471588 0.453613 -2.898224 C 0 -2.526031 -0.030900 0.376572 C 0 -3.634720 -1.080429 -0.019333 C 0 -4.533188 0.657303 -1.806595 C 0 -4.823166 -0.501816 -0.838577 Si 0 -3.237259 1.125305 1.765411 C 0 -4.003952 2.797150 1.264496 C 0 -1.956024 1.546585 3.123657 C 0 -4.595413 0.224000 2.755219 O 0 -0.138519 0.076996 -0.881378 C 0 0.897507 0.337234 -0.148407 C 0 2.210007 0.072220 -0.826111 C 0 0.827942 0.133743 1.351944 C 0 3.426682 0.092850 -0.124619 C 0 2.234177 -0.214966 -2.201935 C 0 3.437256 -0.473511 -2.852921 C 0 4.630585 -0.164551 -0.779449 C 0 4.641769 -0.448532 -2.145477 H 0 -1.795181 -1.661316 -3.792679 H 0 -0.832657 -1.789368 -2.328430 H 0 -1.344406 0.494507 -3.093491 H 0 -3.825165 -2.328461 -2.638641 H 0 -2.560806 -3.507019 -2.386047 H 0 -2.129440 -2.645065 -0.106674 H 0 -3.774094 -3.204025 -0.345856 H 0 -3.853302 -0.249756 -3.653458 H 0 -3.378967 1.413864 -3.425095 H 0 -1.832687 -0.633667 0.988770 H 0 -4.079849 -1.417816 0.924225 H 0 -4.243271 1.530350 -1.212341 H 0 -5.480759 0.937195 -2.289963 H 0 -5.317215 -1.320816 -1.379135 H 0 -5.580400 -0.130646 -0.133804 H 0 -3.281128 3.507004 0.848038 H 0 -4.425446 3.261749 2.165588 H 0 -4.821793 2.694092 0.543442 H 0 -1.541900 0.642715 3.587738

S34

H 0 -2.476318 2.100464 3.915894 H 0 -1.115189 2.170151 2.802780 H 0 -4.239243 -0.723938 3.176788 H 0 -5.492828 0.007996 2.165588 H 0 -4.903397 0.857849 3.596863 H 0 1.612854 0.675995 1.881912 H 0 0.952789 -0.936752 1.565598 H 0 -0.134048 0.449829 1.742172 H 0 3.446426 0.312668 0.937454 H 0 1.297989 -0.241287 -2.747772 H 0 3.434433 -0.699326 -3.915878 H 0 5.560944 -0.143936 -0.218400 H 0 5.580414 -0.650131 -2.654343 C 0 -1.372192 2.288010 -1.093185 C 0 -0.420395 2.704498 -0.119324 C 0 0.941650 2.542862 -0.284561 H 0 -1.023483 2.388702 -2.121582 H 0 -2.379395 2.681564 -0.967621 H 0 -0.784225 2.955811 0.875732 H 0 1.355606 2.506134 -1.287018 H 0 1.633698 2.846420 0.496338 B3LYP/6-31G* Energy = -1287.741132 B3LYP/6-31G* Free Energy = -1287.795231 B3LYP/6-31G* Free energy in solution = -1288.27974 Number of Imaginary Frequencies = 1 (-348.3)

TS-1+4-ReAnti-BC B3LYP/6-31G* Geometry C 0 0.638748 -3.695831 2.199081 C 0 0.657715 -2.147964 2.201202 C 0 -0.741943 -4.356781 2.189209 C 0 -1.627090 -4.027161 0.983643 B 0 0.477158 -1.423355 0.738327 C 0 -0.273026 -1.545822 3.301025 C 0 -0.943634 -1.711273 -0.084305 C 0 -2.005264 -2.542679 0.735687 C 0 -1.600464 -0.939514 2.821930 O 0 0.797546 0.034775 1.044861 C 0 -2.548187 -1.839996 2.017014 Si 0 -1.004364 -2.342712 -1.920013 C 0 1.065857 1.102386 0.361984 C 0 -2.709381 -3.092407 -2.329575 C 0 -0.852402 -0.938721 -3.210052 C 0 0.264740 -3.671295 -2.435959 C 0 1.754913 2.176437 1.150742 C 0 0.138275 1.534790 -0.756058 C 0 1.941910 3.471207 0.639435 C 0 2.221542 1.892975 2.446030 C 0 2.854095 2.874390 3.204102 C 0 2.577530 4.451920 1.400116 C 0 3.036331 4.158539 2.684784 H 0 1.167557 -4.055267 3.095306 H 0 1.220734 -4.073135 1.344849 H 0 1.678391 -1.883926 2.515976 H 0 -0.610580 -5.447571 2.230621 H 0 -1.276489 -4.093719 3.110977 H 0 -2.565613 -4.588547 1.104111 H 0 -1.155640 -4.434769 0.078766 H 0 -0.471237 -2.298508 4.078506 H 0 0.270172 -0.739609 3.812103 H 0 -1.419662 -0.721375 -0.196747

H 0 -2.891296 -2.609940 0.095108 H 0 -2.152115 -0.568512 3.698212 H 0 -1.373260 -0.050064 2.222412 H 0 -2.977509 -2.607391 2.677414 H 0 -3.397919 -1.209152 1.719070 H 0 -3.530182 -2.391556 -2.133743 H 0 -2.922058 -4.013733 -1.776749 H 0 -2.741257 -3.338211 -3.399048 H 0 -1.630157 -0.177368 -3.070572 H 0 -1.007721 -1.373947 -4.205795 H 0 0.113602 -0.424149 -3.237213 H 0 0.352295 -4.484985 -1.706909 H 0 1.269348 -3.269363 -2.606018 H 0 -0.064713 -4.119736 -3.382217 H 0 0.620255 2.223053 -1.452454 H 0 -0.725739 2.050491 -0.314667 H 0 -0.224487 0.676407 -1.312912 H 0 1.596420 3.724900 -0.357071 H 0 2.072418 0.897995 2.849731 H 0 3.202377 2.637451 4.205795 H 0 2.712296 5.447586 0.986343 H 0 3.530167 4.924042 3.277069 C 0 2.033722 -1.836609 -0.133469 C 0 2.282379 -0.822311 -1.102539 C 0 2.828400 0.404831 -0.780594 H 0 2.765533 -1.860840 0.674652 H 0 1.838638 -2.831284 -0.529663 H 0 1.830521 -0.931671 -2.087112 H 0 3.467346 0.491959 0.092270 H 0 2.973984 1.163666 -1.544769 B3LYP/6-31G* Energy = -1287.741696 B3LYP/6-31G* Free Energy = -1287.795819 B3LYP/6-31G* Free energy in solution = -1288.279787 Number of Imaginary Frequencies = 1 (-342.2) TS-1+4-SiSyn-CB B3LYP/6-31G* Geometry C 0 0.360504 -2.404892 -1.790970 C 0 0.135620 -0.881882 -1.595978 C 0 -0.889297 -3.289841 -1.756332 C 0 -1.736954 -3.210556 -0.483307 B 0 -0.089706 -0.393311 -0.040665 C 0 -0.941681 -0.360565 -2.600021 C 0 -1.459061 -0.906937 0.730728 C 0 -2.389435 -1.850494 -0.107100 C 0 -2.327469 -0.033218 -2.024628 Si 0 -2.505447 0.301147 1.798600 C 0 -3.092667 -1.158234 -1.307587 C 0 -4.113876 -0.555634 2.362198 C 0 -3.051208 1.939926 1.001938 C 0 -1.609558 0.677536 3.441483 O 0 0.103546 1.133423 0.107513 C 0 1.000961 2.027603 0.384079 C 0 1.967697 2.483475 -0.678604 C 0 0.539047 3.129166 1.326523 C 0 1.689331 2.235825 -2.028992 C 0 3.097000 3.261307 -0.363052 C 0 3.932632 3.747269 -1.363907 C 0 2.523361 2.728622 -3.033890 C 0 3.650330 3.480560 -2.707031 H 0 0.843582 -2.559158 -2.768234

S35

H 0 1.079544 -2.778992 -1.050003 H 0 1.089523 -0.428543 -1.902542 H 0 -0.577896 -4.334808 -1.898041 H 0 -1.524200 -3.059143 -2.621658 H 0 -2.550583 -3.943115 -0.593781 H 0 -1.141571 -3.558289 0.374496 H 0 -1.047943 -1.075363 -3.428955 H 0 -0.582260 0.562576 -3.075760 H 0 -1.106140 -1.563965 1.547882 H 0 -3.202942 -2.153564 0.564300 H 0 -2.215744 0.809311 -1.333710 H 0 -2.962372 0.338058 -2.842500 H 0 -3.396225 -1.922485 -2.037018 H 0 -4.033356 -0.716675 -0.948303 H 0 -3.917800 -1.512970 2.861100 H 0 -4.806595 -0.750381 1.535233 H 0 -4.639618 0.085205 3.082108 H 0 -3.515335 2.587051 1.757721 H 0 -3.799393 1.769913 0.218964 H 0 -2.220322 2.489532 0.551620 H 0 -2.235458 1.319626 4.074249 H 0 -0.642517 1.176025 3.328308 H 0 -1.434402 -0.251541 3.999725 H 0 -0.024139 2.719315 2.163910 H 0 -0.123566 3.801819 0.764755 H 0 1.370911 3.728119 1.701355 H 0 0.801147 1.677490 -2.289536 H 0 3.339844 3.469849 0.674652 H 0 4.806610 4.334793 -1.096085 H 0 2.283707 2.526093 -4.074249 H 0 4.302094 3.861267 -3.488556 C 0 1.383011 -1.033783 0.827896 C 0 1.665939 -0.150681 1.904100 C 0 2.442245 0.979752 1.746200 H 0 2.169357 -1.067673 0.070267 H 0 1.048203 -2.031174 1.112473 H 0 1.063644 -0.242630 2.807816 H 0 3.223740 0.977264 0.995010 H 0 2.588669 1.663574 2.578232 B3LYP/6-31G* Energy = -1287.735086 B3LYP/6-31G* Free Energy = -1287.789889 B3LYP/6-31G* Free energy in solution = -1288.272768 Number of Imaginary Frequencies = 1 (-368.3)

TS-1+4-SiSyn-BC B3LYP/6-31G* Geometry C 0 1.554352 -3.239900 -0.293457 C 0 1.414444 -1.690796 -0.352356 C 0 0.256592 -4.062027 -0.225769 C 0 -0.806030 -3.826904 -1.309418 B 0 0.098312 -1.046860 0.386520 C 0 1.652023 -1.145218 -1.786819 C 0 -1.384079 -1.520493 -0.190796 C 0 -1.337448 -2.375198 -1.513290 C 0 0.820800 -1.772339 -2.906738 Si 0 -2.867554 -0.309280 -0.280563 C 0 -0.696960 -1.662811 -2.734680 C 0 -4.354324 -1.110336 -1.167068 C 0 -2.540054 1.314148 -1.224213 C 0 -3.563919 0.016129 1.469910 O 0 0.388351 0.469559 0.446671

C 0 0.538696 1.497116 1.220840 C 0 1.846832 2.234634 1.110886 C 0 -0.687164 2.342911 1.530700 C 0 2.906036 1.684387 0.371078 C 0 2.039902 3.486877 1.720795 C 0 3.252853 4.162292 1.596664 C 0 4.117050 2.361359 0.246719 C 0 4.297729 3.602859 0.859512 H 0 2.157196 -3.585892 -1.146271 H 0 2.141907 -3.512115 0.594727 H 0 2.266693 -1.302261 0.227936 H 0 -0.210846 -3.898132 0.752823 H 0 0.522903 -5.129059 -0.240051 H 0 -0.445175 -4.214905 -2.272324 H 0 -1.662216 -4.464127 -1.046097 H 0 2.714218 -1.287689 -2.044540 H 0 1.481567 -0.059998 -1.791168 H 0 -1.781708 -2.220642 0.566010 H 0 -2.379166 -2.525635 -1.819763 H 0 1.096313 -1.291992 -3.856613 H 0 1.098877 -2.827789 -3.024155 H 0 -1.159744 -2.080887 -3.640839 H 0 -0.976700 -0.600067 -2.719727 H 0 -4.592377 -2.102066 -0.762619 H 0 -4.201752 -1.219193 -2.246704 H 0 -5.242447 -0.479767 -1.027420 H 0 -1.529190 1.701523 -1.073898 H 0 -3.253876 2.096542 -0.936203 H 0 -2.664764 1.146423 -2.301025 H 0 -4.321625 0.809753 1.447144 H 0 -2.828842 0.286728 2.233337 H 0 -4.064438 -0.895142 1.822600 H 0 -0.575790 2.930878 2.443115 H 0 -1.568878 1.714859 1.624115 H 0 -0.852081 3.041672 0.701080 H 0 2.766571 0.727814 -0.114655 H 0 1.246200 3.944885 2.300751 H 0 3.379379 5.129059 2.076400 H 0 4.920334 1.918655 -0.335983 H 0 5.242447 4.130676 0.761948 C 0 0.271713 -1.516891 2.158875 C 0 0.011566 -0.406921 3.014100 C 0 0.913010 0.621033 3.194672 H 0 1.311020 -1.848816 2.198013 H 0 -0.418488 -2.350174 2.284775 H 0 -1.009216 -0.257477 3.367981 H 0 1.968048 0.438431 3.015854 H 0 0.686188 1.451447 3.856598 B3LYP/6-31G* Energy = -1287.733876 B3LYP/6-31G* Free Energy = -1287.790519 B3LYP/6-31G* Free energy in solution = -1288.271705 Number of Imaginary Frequencies = 1 (-359.1) Product P-1+4-R (Global minimum)

B3LYP/6-31G* Geometry C 0 -0.846268 -4.350296 1.246155 C 0 -0.846268 -3.016281 1.246155 C 0 0.389496 -2.159607 1.274597 C 0 0.497574 -1.130600 0.108124 O 0 -0.657822 -0.270325 0.272980 C 0 1.801239 -0.343811 0.294830

S36

C 0 0.403152 -1.867554 -1.233398 B 0 -1.085922 0.809692 -0.466736 C 0 1.903793 0.579865 1.346542 C 0 2.931747 -0.562042 -0.503052 C 0 -0.281403 1.438690 -1.694031 C 0 -2.515182 1.356598 -0.036697 C 0 3.088700 1.274612 1.582932 C 0 4.121811 0.131332 -0.267334 C 0 -0.963852 1.053619 -3.047440 C 0 -0.065048 2.974640 -1.550735 C 0 -3.193436 2.347870 -1.029388 Si 0 -2.628311 1.900177 1.808655 C 0 4.205521 1.053741 0.774170 C 0 -2.456284 0.679230 -2.967804 C 0 -3.448990 1.732407 -2.439850 C 0 -1.240417 3.880081 -1.938431 C 0 -2.522186 3.742157 -1.107742 C 0 -1.216309 3.038391 2.382263 C 0 -2.625107 0.359421 2.913605 C 0 -4.268143 2.810913 2.118546 H 0 -1.770264 -4.922775 1.246155 H 0 0.078690 -4.924210 1.255753 H 0 -1.793335 -2.479034 1.239853 H 0 0.416382 -1.588272 2.212051 H 0 1.286987 -2.789490 1.261566 H 0 -0.593292 -2.304688 -1.334259 H 0 1.126312 -2.688354 -1.278885 H 0 0.583115 -1.202164 -2.079987 H 0 1.044495 0.755707 1.985687 H 0 2.894653 -1.273087 -1.321838 H 0 0.728729 1.015060 -1.711517 H 0 -3.146454 0.449234 0.001816 H 0 3.139526 1.988281 2.401154 H 0 4.983185 -0.052582 -0.904190 H 0 -0.821548 1.857681 -3.782089 H 0 -0.444794 0.183273 -3.468826 H 0 0.785995 3.254181 -2.188721 H 0 0.250778 3.207336 -0.523500 H 0 -4.193741 2.556610 -0.627045 H 0 5.130432 1.594376 0.955795 H 0 -2.551102 -0.228867 -2.353943 H 0 -2.790924 0.381363 -3.971436 H 0 -3.536346 2.548370 -3.171387 H 0 -4.434692 1.247238 -2.427277 H 0 -0.903885 4.924194 -1.871338 H 0 -1.481339 3.723557 -2.997574 H 0 -2.325989 4.101151 -0.088989 H 0 -3.260544 4.440200 -1.528503 H 0 -1.261887 4.029144 1.916138 H 0 -0.227356 2.620468 2.162552 H 0 -1.275620 3.186920 3.468200 H 0 -3.465744 -0.303436 2.673096 H 0 -2.716370 0.636139 3.971436 H 0 -1.704666 -0.219040 2.790680 H 0 -4.337738 3.758804 1.572952 H 0 -4.373535 3.038925 3.186905 H 0 -5.130417 2.197662 1.828888 B3LYP/6-31G* Energy = -1287.815395 B3LYP/6-31G* Free Energy = -1287.873678 B3LYP/6-31G* Free energy in solution = -1288.350695 Number of Imaginary Frequencies = 0

Product P-1+4-R (from IRC of TS-1+4-ReSyn-CB)

B3LYP/6-31G* Geometry O 0 0.229691 0.305800 0.034042 C 0 0.229691 1.738083 0.034042 B 0 -0.650925 -0.747574 0.034042 C 0 1.035187 2.228287 1.248596 C 0 -1.167297 2.385437 0.061829 C 0 -2.209152 -0.643509 0.387009 C 0 -0.000015 -2.109406 -0.481461 C 0 0.987213 2.125778 -1.276993 C 0 1.311493 3.595779 1.408585 C 0 1.494812 1.345215 2.231323 C 0 -3.052582 -0.782867 -0.919769 C 0 -2.691742 -1.612167 1.510071 C 0 -0.983871 -3.298477 -0.699173 Si 0 1.709824 -2.626556 0.241241 C 0 0.285950 1.738373 -2.550476 C 0 2.028397 4.061539 2.509735 C 0 2.212448 1.809250 3.336426 C 0 -3.286041 -2.208588 -1.432007 C 0 -2.038208 -3.018097 -1.804474 C 0 -1.839554 -2.864990 1.767715 C 0 -1.616302 -3.853638 0.609650 C 0 3.045013 -1.382767 -0.277527 C 0 2.204727 -4.306915 -0.501434 C 0 1.794479 -2.821991 2.131454 C 0 0.738235 0.835861 -3.423035 C 0 2.484161 3.168442 3.481186 H 0 -1.814377 1.980759 -0.720093 H 0 -1.069305 3.463318 -0.104660 H 0 -1.651031 2.247100 1.031265 H 0 -2.423340 0.361038 0.755829 H 0 0.347977 -1.814514 -1.490784 H 0 1.973907 1.653534 -1.235947 H 0 1.147202 3.211578 -1.268967 H 0 0.965637 4.313705 0.669693 H 0 1.292130 0.286865 2.128342 H 0 -4.038559 -0.329987 -0.738602 H 0 -2.593674 -0.187424 -1.723846 H 0 -3.735107 -1.903580 1.324081 H 0 -2.713852 -1.052597 2.454834 H 0 -0.394867 -4.125824 -1.116013 H 0 -0.647400 2.257294 -2.771317 H 0 2.230072 5.125092 2.607544 H 0 2.559647 1.100311 4.083694 H 0 -3.931046 -2.149811 -2.320023 H 0 -3.869324 -2.767288 -0.689102 H 0 -1.529770 -2.532089 -2.650360 H 0 -2.386307 -3.990219 -2.183594 H 0 -2.292465 -3.421097 2.600906 H 0 -0.860748 -2.536972 2.137619 H 0 -0.966827 -4.649628 1.000259 H 0 -2.564087 -4.352646 0.363846 H 0 2.896591 -0.403381 0.186539 H 0 3.052536 -1.238068 -1.365112 H 0 4.038559 -1.748123 0.011993 H 0 1.557220 -5.125092 -0.165283 H 0 3.230133 -4.559494 -0.202835 H 0 2.177582 -4.292816 -1.598083 H 0 2.829849 -3.038254 2.425247 H 0 1.174896 -3.651749 2.490082 H 0 1.485840 -1.920700 2.673447

S37

H 0 0.201218 0.605774 -4.339600 H 0 1.670670 0.300430 -3.257324 H 0 3.043961 3.529739 4.339584 B3LYP/6-31G* Energy = -1287.805266 B3LYP/6-31G* Free Energy = -1287.863465 B3LYP/6-31G* Free energy in solution = -1288.341288 Number of Imaginary Frequencies = 0 Product P-1+4-S (Global minimum)

B3LYP/6-31G* Geometry C 0 -2.644531 -4.094940 1.416840 C 0 -2.644531 -2.760635 1.416840 C 0 -1.408722 -1.905045 1.444031 C 0 -1.221924 -0.960785 0.215454 O 0 -0.014053 -0.230500 0.545700 C 0 -2.417847 -0.006302 0.119263 C 0 -0.982529 -1.810318 -1.038437 B 0 0.614639 0.804062 -0.109879 C 0 -3.404312 -0.130051 -0.867172 C 0 -2.575180 0.995209 1.091003 C 0 0.101578 1.452667 -1.476181 C 0 1.910309 1.337402 0.642471 C 0 -4.508392 0.726471 -0.889740 C 0 -3.675659 1.850677 1.071045 C 0 -0.392700 2.920685 -1.266281 C 0 1.157104 1.333435 -2.615997 C 0 2.601776 2.582626 0.015732 Si 0 3.116791 -0.078156 1.147598 C 0 -4.648743 1.720367 0.077591 C 0 0.180695 3.671204 -0.051224 C 0 1.706161 3.859726 0.041748 C 0 2.305862 2.348419 -2.600677 C 0 3.230789 2.324219 -1.377594 C 0 2.498276 -0.879456 2.751617 C 0 4.850952 0.615707 1.503998 C 0 3.288605 -1.431656 -0.175476 H 0 -3.568710 -4.666916 1.416840 H 0 -1.719269 -4.667969 1.427032 H 0 -3.596893 -2.230698 1.411224 H 0 -1.422211 -1.266464 2.337189 H 0 -0.514984 -2.535995 1.515915 H 0 -1.793213 -2.530228 -1.182800 H 0 -0.887466 -1.202682 -1.941315 H 0 -0.055969 -2.377869 -0.907425 H 0 -3.318604 -0.895554 -1.631271 H 0 -1.822174 1.108826 1.865265 H 0 -0.769897 0.894150 -1.832184 H 0 1.538147 1.635834 1.640228 H 0 -5.257843 0.613281 -1.668716 H 0 -3.772476 2.620377 1.832291 H 0 -0.215256 3.505569 -2.179688 H 0 -1.481277 2.897675 -1.136658 H 0 0.631714 1.448380 -3.575592 H 0 1.575729 0.315521 -2.629395 H 0 3.460342 2.824448 0.655884 H 0 -5.506714 2.386917 0.059479 H 0 -0.164688 3.162430 0.860062 H 0 -0.281311 4.667953 -0.015015 H 0 1.895935 4.389694 0.985321 H 0 2.038589 4.547073 -0.749084 H 0 1.894500 3.358841 -2.719879

H 0 2.921524 2.180161 -3.495500 H 0 4.002350 3.090881 -1.539673 H 0 3.768127 1.365982 -1.356171 H 0 1.481674 -1.267822 2.636200 H 0 2.486282 -0.154785 3.575592 H 0 3.149292 -1.709442 3.053925 H 0 5.324478 1.053467 0.618073 H 0 5.506700 -0.187698 1.863342 H 0 4.825226 1.388412 2.282166 H 0 2.330673 -1.931671 -0.357086 H 0 4.003860 -2.196869 0.151413 H 0 3.646118 -1.037460 -1.133987 B3LYP/6-31G* Energy = -1287.816635 B3LYP/6-31G* Free Energy = -1287.875183 B3LYP/6-31G* Free energy in solution = -1288.351744 Number of Imaginary Frequencies = 0 Product P-1+4-S (from IRC of TS-1+4-SiAnti-CB)

B3LYP/6-31G* Geometry O 0 -0.222229 0.378311 -0.413574 C 0 -0.222229 1.814362 -0.413574 B 0 -1.144806 -0.642609 -0.413574 C 0 1.150513 2.243805 -0.977203 C 0 -1.294373 2.422668 -1.340836 C 0 -2.729431 -0.444794 -0.510864 C 0 -0.472733 -2.086380 -0.509125 C 0 -0.355179 2.302856 1.058533 C 0 1.586426 3.574387 -0.875076 C 0 1.963730 1.338104 -1.668503 C 0 -3.168686 -0.708252 -1.987671 C 0 -3.592255 -1.246658 0.507080 C 0 -1.433044 -3.254929 -0.889603 Si 0 0.839233 -2.524445 0.840408 C 0 -1.652557 2.001190 1.756012 C 0 3.180161 1.742203 -2.222961 C 0 2.802094 3.979828 -1.425217 C 0 -3.327896 -2.176971 -2.398087 C 0 -2.081284 -3.064377 -2.288620 C 0 -2.957200 -2.496567 1.134583 C 0 -2.472885 -3.623367 0.207153 C 0 0.353180 -2.139053 2.637314 C 0 2.451721 -1.592224 0.487930 C 0 1.247604 -4.379761 0.752563 C 0 -1.755569 1.357895 2.920975 C 0 3.608368 3.063095 -2.101242 H 0 -1.217773 1.975784 -2.336761 H 0 -1.118805 3.497742 -1.445908 H 0 -2.311951 2.282059 -0.974731 H 0 -2.964462 0.606018 -0.327179 H 0 0.217255 -1.981155 -1.368088 H 0 0.479324 1.876709 1.626617 H 0 -0.213150 3.391113 1.060257 H 0 0.975800 4.315674 -0.366745 H 0 1.640671 0.309692 -1.766312 H 0 -2.467178 -0.217941 -2.679352 H 0 -4.137009 -0.211670 -2.148361 H 0 -3.838409 -0.576294 1.340729 H 0 -4.556320 -1.507370 0.047256 H 0 -0.806870 -4.148102 -1.015091 H 0 -2.559952 2.386841 1.291656 H 0 3.793594 1.016541 -2.750961

S38

H 0 3.116623 5.015457 -1.325165 H 0 -3.671829 -2.202133 -3.441696 H 0 -4.141891 -2.627319 -1.816086 H 0 -1.309692 -2.693436 -2.980026 H 0 -2.362091 -4.059982 -2.662384 H 0 -2.114014 -2.165924 1.749832 H 0 -3.680618 -2.930100 1.840088 H 0 -3.336990 -4.107468 -0.268997 H 0 -2.035583 -4.394760 0.856308 H 0 -0.021896 -1.116211 2.752060 H 0 1.237305 -2.241074 3.279785 H 0 -0.411652 -2.820465 3.025970 H 0 2.324051 -0.508331 0.562485 H 0 2.832779 -1.809800 -0.517670 H 0 3.227661 -1.892273 1.203751 H 0 0.394257 -5.015457 1.015594 H 0 2.056671 -4.612244 1.456757 H 0 1.588943 -4.678146 -0.246246 H 0 -2.715591 1.203720 3.406235 H 0 -0.881500 0.972687 3.441696 H 0 4.556335 3.376862 -2.529953 B3LYP/6-31G* Energy = -1287.806157 B3LYP/6-31G* Free Energy = -1287.863304 B3LYP/6-31G* Free energy in solution = -1288.344195 Number of Imaginary Frequencies = 0 Allylboration Reaction between 2 and 4 Complex (2-4)-ReSyn-CB B3LYP/6-31G* Geometry O 0 -1.479813 0.727081 -2.515106 C 0 -0.376129 1.004532 -3.029251 C 0 -0.146088 2.410019 -3.431122 C 0 0.673096 -0.033630 -3.336197 C 0 0.976974 2.783951 -4.192581 C 0 -1.073792 3.396530 -3.047195 C 0 1.165405 4.112274 -4.563293 C 0 -0.876602 4.723236 -3.415207 C 0 0.240402 5.084274 -4.173416 B 0 -2.193451 -0.398483 -1.500931 C 0 -1.845779 -1.922241 -1.964478 C 0 -3.812622 -0.011841 -1.469177 C 0 -1.486938 0.077713 -0.075745 C 0 -2.494797 -2.985779 -1.026047 C 0 -2.109024 -2.241043 -3.465851 C 0 -4.823654 -1.029755 -2.103348 C 0 -4.145432 1.436279 -1.798218 C 0 0.000000 0.000000 0.000000 C 0 -3.947571 -3.387238 -1.312225 C 0 -5.002747 -2.281311 -1.204071 C 0 -3.195648 -1.409149 -4.170547 C 0 -4.620316 -1.436005 -3.594254 C 0 -4.447403 1.888870 -3.095886 C 0 -4.182007 2.398453 -0.771255 C 0 0.842102 1.043472 -0.000015 C 0 -4.486023 3.738068 -1.021515 C 0 -4.763245 3.224365 -3.352783 C 0 -4.781418 4.161728 -2.318512 H 0 0.683548 -0.219116 -4.418884 H 0 0.460846 -0.966431 -2.822906 H 0 1.665054 0.319214 -3.046906

H 0 1.703369 2.040802 -4.503983 H 0 -1.938187 3.111786 -2.460205 H 0 2.033340 4.389786 -5.154373 H 0 -1.600555 5.473373 -3.111511 H 0 0.391312 6.121475 -4.460434 H 0 -0.767761 -2.078720 -1.802353 H 0 -4.032715 -0.090622 -0.393875 H 0 -1.923889 -0.575577 0.695038 H 0 -1.810150 1.099472 0.161179 H 0 -1.893967 -3.906158 -1.084152 H 0 -2.417130 -2.652252 0.018646 H 0 -2.328751 -3.311325 -3.591797 H 0 -1.182007 -2.080078 -4.033752 H 0 -5.801636 -0.528351 -2.063828 H 0 0.432007 -1.003128 0.023621 H 0 -4.005844 -3.843475 -2.308884 H 0 -4.223100 -4.189911 -0.613220 H 0 -5.080276 -1.954407 -0.156876 H 0 -5.975937 -2.731369 -1.449020 H 0 -3.254349 -1.740616 -5.217880 H 0 -2.858521 -0.366547 -4.212097 H 0 -5.230881 -0.778580 -4.227051 H 0 -5.047470 -2.438049 -3.740829 H 0 -4.439941 1.190475 -3.924759 H 0 -3.982635 2.084869 0.250809 H 0 0.477417 2.069183 -0.000015 H 0 1.921295 0.912994 0.035233 H 0 -4.508316 4.446686 -0.196655 H 0 -4.997437 3.531540 -4.369507 H 0 -5.034470 5.200104 -2.517410 B3LYP/6-31G* Energy = -1110.164349 B3LYP/6-31G* Free Energy = -1110.218944 B3LYP/6-31G* Free energy in solution = -1110.686709 Number of Imaginary Frequencies = 0 HOMO = -5.72 LUMO = -2.35

Complex (2-4)-ReSyn-BC B3LYP/6-31G* Geometry O 0 -1.229294 0.219254 0.000000 C 0 0.000000 0.000000 0.000000 C 0 0.900986 1.173904 -0.000015 C 0 0.592896 -1.384415 -0.077606 C 0 2.286346 1.038589 -0.208786 C 0 0.360870 2.456467 0.210709 C 0 3.110123 2.160461 -0.211349 C 0 1.190292 3.572952 0.214661 C 0 2.564026 3.428864 0.002594 B 0 -2.684555 -0.501404 0.410156 C 0 -2.776688 -2.008026 -0.225082 C 0 -3.845810 0.583694 -0.089600 C 0 -2.548965 -0.472397 2.063171 C 0 -4.139389 -2.728653 0.037354 C 0 -2.362839 -2.148041 -1.713272 C 0 -4.652725 0.174911 -1.362625 C 0 -3.439270 2.053314 -0.072296 C 0 -1.406600 -1.222260 2.662460 C 0 -5.425491 -1.880859 0.119827 C 0 -5.745483 -0.878326 -1.008438 C 0 -3.394424 -1.696945 -2.747513 C 0 -3.832443 -0.234711 -2.620377

S39

C 0 -3.518692 2.780334 1.131882 C 0 -3.012817 2.768066 -1.206543 C 0 -0.324387 -0.675171 3.233841 C 0 -2.670990 4.120804 -1.138748 C 0 -3.167831 4.128586 1.211000 C 0 -2.737778 4.811768 0.071747 H 0 -0.158752 -2.142151 0.119797 H 0 1.412125 -1.493591 0.636276 H 0 0.999359 -1.543594 -1.085419 H 0 2.725021 0.061005 -0.377884 H 0 -0.704453 2.562531 0.373200 H 0 4.177200 2.046249 -0.378677 H 0 0.759171 4.555603 0.380539 H 0 3.209625 4.303024 0.004578 H 0 -2.045837 -2.623352 0.322922 H 0 -4.579529 0.522186 0.726654 H 0 -3.494385 -0.899490 2.433517 H 0 -2.514984 0.566910 2.411194 H 0 -4.274078 -3.513748 -0.721725 H 0 -4.071396 -3.267303 0.992676 H 0 -2.122879 -3.204041 -1.915695 H 0 -1.434387 -1.590363 -1.897980 H 0 -5.203400 1.073532 -1.674942 H 0 -1.452332 -2.311890 2.598251 H 0 -6.276993 -2.571503 0.203003 H 0 -5.412857 -1.333771 1.070190 H 0 -6.647995 -0.337891 -0.691284 H 0 -6.037994 -1.421356 -1.917252 H 0 -2.968552 -1.842468 -3.750656 H 0 -4.271744 -2.353745 -2.706070 H 0 -2.936584 0.393082 -2.703522 H 0 -4.447693 0.003677 -3.500122 H 0 -3.884918 2.280000 2.024719 H 0 -2.952591 2.271988 -2.167984 H 0 -0.225525 0.402771 3.349823 H 0 0.484543 -1.281891 3.634400 H 0 -2.353409 4.635864 -2.042557 H 0 -3.249908 4.649307 2.162354 H 0 -2.477951 5.866089 0.123138 B3LYP/6-31G* Energy = -1110.162353 B3LYP/6-31G* Free Energy = -1110.217237 B3LYP/6-31G* Free energy in solution = -1110.684676 Number of Imaginary Frequencies = 0 HOMO = -5.71 LUMO = -2.37 Complex (2-4)-SiAnti-CB B3LYP/6-31G* Geometry O 0 1.126678 0.483795 0.000000 C 0 0.000000 0.000000 0.000000 C 0 -1.206009 0.887054 0.000015 C 0 -0.187820 -1.505478 -0.007889 C 0 -2.514679 0.379791 0.007843 C 0 -1.013153 2.278229 -0.012161 C 0 -2.103226 3.142258 -0.014481 C 0 -3.607239 1.246231 0.005539 C 0 -3.403214 2.627289 -0.005066 B 0 4.278397 -0.292633 -0.326126 C 0 4.229584 -1.086304 -1.699829 C 0 4.428055 1.293396 -0.353500 C 0 4.221848 -1.043274 1.078369

C 0 5.718277 -1.311295 -2.131485 C 0 3.347885 -0.474213 -2.824631 C 0 5.154282 1.885529 -1.611176 C 0 4.841766 1.934311 0.961884 C 0 4.005005 -2.528458 1.080811 C 0 6.725876 -0.262772 -1.612579 C 0 6.509674 1.213287 -1.996002 C 0 3.926224 0.705460 -3.616943 C 0 4.203705 1.990585 -2.829132 C 0 6.184860 2.116348 1.330307 C 0 3.858444 2.360474 1.871185 C 0 2.996704 -3.171967 1.676086 C 0 4.197998 2.938721 3.094345 C 0 6.529800 2.698807 2.551682 C 0 5.538727 3.112976 3.441803 H 0 0.790009 -1.987366 0.043457 H 0 -0.705811 -1.826477 -0.919968 H 0 -0.796875 -1.831924 0.843246 H 0 -2.686981 -0.691864 0.015320 H 0 0.003159 2.657776 -0.021545 H 0 -1.943542 4.216919 -0.024078 H 0 -4.616394 0.843948 0.012009 H 0 -4.255264 3.301834 -0.006592 H 0 3.803009 -2.079681 -1.508087 H 0 3.362930 1.556763 -0.481842 H 0 5.171539 -0.805878 1.590073 H 0 3.458435 -0.545593 1.694382 H 0 5.787170 -1.384430 -3.225616 H 0 6.049881 -2.285370 -1.749039 H 0 3.128342 -1.272873 -3.549133 H 0 2.378555 -0.182449 -2.397003 H 0 5.393112 2.925980 -1.353668 H 0 4.748077 -3.123032 0.544617 H 0 7.730515 -0.552826 -1.950485 H 0 6.764908 -0.333435 -0.514100 H 0 7.328781 1.779831 -1.534195 H 0 6.661194 1.327393 -3.078384 H 0 4.847336 0.384949 -4.121490 H 0 3.224976 0.949020 -4.427414 H 0 3.250839 2.422668 -2.491867 H 0 4.635574 2.721252 -3.528381 H 0 6.977127 1.804092 0.656418 H 0 2.810287 2.231598 1.609253 H 0 2.234955 -2.636444 2.240311 H 0 2.900650 -4.254074 1.635513 H 0 3.412400 3.259460 3.774475 H 0 7.579102 2.828537 2.806198 H 0 5.807297 3.567291 4.391907 B3LYP/6-31G* Energy = -1110.173176 B3LYP/6-31G* Free Energy = -1110.236169 B3LYP/6-31G* Free energy in solution = -1110.687364 Number of Imaginary Frequencies = 0 HOMO = -5.86 LUMO = -1.74 Complex (2-4)-SiAnti-BC B3LYP/6-31G* Geometry B 0 -0.000641 2.162277 0.927170 C 0 -0.000641 3.748260 0.927170 C 0 -1.350479 1.322327 0.927170 C 0 1.399780 1.391602 0.846710

S40

C 0 -0.621400 4.298828 2.248047 C 0 -0.659622 4.360672 -0.348206 C 0 -2.683258 2.134308 0.966858 C 0 -1.364639 0.149109 1.899628 C 0 2.302094 1.676758 2.019241 C 0 -2.153030 4.321960 2.339127 C 0 -2.876221 2.970673 2.253952 C 0 -1.673035 3.474747 -1.098846 C 0 -2.910461 2.961472 -0.334610 C 0 -0.895218 0.257156 3.219086 C 0 -1.884567 -1.093582 1.498596 C 0 3.364349 2.486954 2.021744 C 0 -1.931671 -2.180969 2.371872 C 0 -0.939255 -0.826828 4.098907 C 0 -1.457703 -2.051880 3.678970 H 0 1.044067 4.087509 0.942322 H 0 -1.299881 0.860657 -0.075577 H 0 1.258530 0.307846 0.746246 H 0 1.891098 1.745834 -0.073624 H 0 -0.264877 5.331024 2.380188 H 0 -0.215302 3.742157 3.106979 H 0 -1.122681 5.325775 -0.097244 H 0 0.138077 4.598800 -1.063995 H 0 -3.490707 1.388611 0.994019 H 0 2.030609 1.174225 2.949127 H 0 -2.428528 4.794357 3.292542 H 0 -2.547577 4.989532 1.562271 H 0 -2.607010 2.354370 3.122009 H 0 -3.952316 3.170517 2.359085 H 0 -1.139221 2.613556 -1.522964 H 0 -2.037231 4.040466 -1.968338 H 0 -3.468933 2.333969 -1.042374 H 0 -3.575958 3.805420 -0.105743 H 0 -0.485840 1.202744 3.566849 H 0 -2.261826 -1.203339 0.483841 H 0 3.691193 3.006729 1.123047 H 0 3.952316 2.655075 2.920456 H 0 -2.340973 -3.129120 2.031326 H 0 -0.566193 -0.711533 5.113541 H 0 -1.492538 -2.896423 4.362152 O 0 -0.100159 0.217163 -2.172287 C 0 0.608414 -0.416656 -2.944153 C 0 1.094864 -1.786728 -2.588669 C 0 1.006927 0.184555 -4.281494 C 0 1.901093 -2.546005 -3.451202 C 0 0.730759 -2.325394 -1.343567 C 0 1.165344 -3.592758 -0.968918 C 0 2.334976 -3.816818 -3.075638 C 0 1.968475 -4.341293 -1.834610 H 0 2.097031 0.264404 -4.367950 H 0 0.563889 1.178238 -4.364807 H 0 0.658218 -0.438583 -5.113556 H 0 2.194382 -2.149628 -4.418320 H 0 0.107391 -1.734222 -0.681396 H 0 0.879944 -3.996643 -0.001556 H 0 2.959213 -4.396378 -3.750031 H 0 2.308762 -5.331039 -1.541855 B3LYP/6-31G* Energy = -1110.172588 B3LYP/6-31G* Free Energy = -1110.237069 B3LYP/6-31G* Free energy in solution = -1110.683318 Number of Imaginary Frequencies = 0 HOMO = -6.12

LUMO = -1.66

TS-2+4-ReSyn-CB B3LYP/6-31G* Geometry O 0 -0.270050 0.207321 0.350464 C 0 -0.272018 1.509125 0.382675 B 0 -1.340881 -0.852646 0.425919 C 0 0.969238 2.138962 -0.176636 C 0 -2.288727 -0.844025 1.758530 C 0 -0.690567 -2.335403 0.046051 C 0 -0.975937 2.247391 1.508530 C 0 -3.417480 -1.918060 1.764800 C 0 -1.458160 -0.872375 3.078461 C 0 -0.641907 -3.413910 1.189438 C 0 0.604568 -2.279312 -0.748917 C 0 1.316177 3.471146 0.105164 C 0 1.819412 1.384186 -1.003754 C 0 -3.054000 -3.331635 2.236679 C 0 -2.022629 -4.087357 1.394547 C 0 -0.075562 -1.547546 3.006775 C 0 -0.001678 -3.015976 2.553986 C 0 1.870407 -2.159851 -0.147095 C 0 0.576324 -2.368942 -2.152512 C 0 2.479965 4.030548 -0.422043 C 0 2.979416 1.946289 -1.528687 C 0 1.742325 -2.325653 -2.919739 C 0 3.041443 -2.131027 -0.905700 C 0 3.315842 3.271667 -1.241700 C 0 2.986572 -2.208435 -2.299057 H 0 -2.849243 0.102463 1.769485 H 0 -1.421112 -2.760544 -0.657181 H 0 -0.326752 2.239609 2.394424 H 0 -1.916748 1.771042 1.770294 H 0 -1.176437 3.287766 1.247574 H 0 -4.222046 -1.561157 2.425446 H 0 -3.872375 -1.986938 0.765793 H 0 -2.049088 -1.326706 3.886719 H 0 -1.279297 0.160400 3.405838 H 0 -0.008347 -4.219208 0.791321 H 0 0.687973 4.083252 0.742844 H 0 1.568268 0.354126 -1.222260 H 0 -2.706985 -3.287262 3.276947 H 0 -3.976089 -3.929428 2.266556 H 0 -2.453674 -4.313324 0.408173 H 0 -1.851578 -5.061295 1.875992 H 0 0.386749 -1.485107 4.002716 H 0 0.562866 -0.946915 2.348648 H 0 1.062347 -3.286133 2.535431 H 0 -0.439072 -3.654831 3.334366 H 0 1.946884 -2.083984 0.931854 H 0 -0.381012 -2.495041 -2.654068 H 0 2.732330 5.061310 -0.188217 H 0 3.623428 1.340607 -2.160034 H 0 1.676758 -2.400650 -4.002731 H 0 4.001984 -2.044083 -0.403076 H 0 4.222046 3.708893 -1.652374 H 0 3.898880 -2.189300 -2.889694 C 0 -2.313736 -0.376587 -1.042877 C 0 -2.562485 1.022720 -0.947021 C 0 -1.618393 1.970016 -1.290833 H 0 -3.195740 -1.014343 -0.971039 H 0 -1.669922 -0.659515 -1.877014

S41

H 0 -3.428909 1.348679 -0.369736 H 0 -0.860184 1.721695 -2.026276 H 0 -1.825653 3.029907 -1.171844 B3LYP/6-31G* Energy = -1110.154267 B3LYP/6-31G* Free Energy = -1110.206516 B3LYP/6-31G* Free energy in solution = -1110.678038 Number of Imaginary Frequencies = 1 (-349.1) TS-2+4-ReSyn-BC B3LYP/6-31G* Geometry O 0 -0.200821 0.159470 0.234070 C 0 -0.202744 1.462540 0.268661 B 0 -1.266418 -0.903763 0.310715 C 0 1.023438 2.094116 -0.321289 C 0 -2.183762 -0.891739 1.670532 C 0 -0.603928 -2.370819 -0.107910 C 0 -0.879211 2.206253 1.408783 C 0 -3.307800 -1.972000 1.770111 C 0 -1.337372 -0.856400 2.972122 C 0 -0.460815 -3.388153 1.074722 C 0 0.631424 -2.304718 -0.996735 C 0 1.388748 3.419159 -0.029343 C 0 1.839005 1.348785 -1.190506 C 0 -3.107117 -3.337570 1.081238 C 0 -1.807205 -4.127319 1.334641 C 0 -0.734100 -2.189087 3.419128 C 0 0.180344 -2.865555 2.391785 C 0 0.483765 -2.381927 -2.394608 C 0 1.946152 -2.195969 -0.508957 C 0 2.537216 3.980408 -0.587570 C 0 2.983475 1.912521 -1.746536 C 0 3.046646 -2.162811 -1.367188 C 0 1.577255 -2.332397 -3.261063 C 0 3.338547 3.230789 -1.449036 C 0 2.871323 -2.223373 -2.750961 H 0 -2.736465 0.059219 1.675049 H 0 -1.359787 -2.826019 -0.760757 H 0 -1.804962 1.723129 1.707642 H 0 -1.099396 3.240524 1.139069 H 0 -0.203751 2.219116 2.274414 H 0 -3.538025 -2.138870 2.832855 H 0 -4.232559 -1.554626 1.346771 H 0 -1.966782 -0.479980 3.793991 H 0 -0.520386 -0.131607 2.859772 H 0 0.235336 -4.160477 0.719315 H 0 0.787430 4.023788 0.640533 H 0 1.572845 0.324371 -1.417557 H 0 -3.950729 -3.982468 1.366287 H 0 -3.215607 -3.196625 -0.001221 H 0 -1.847397 -5.005402 0.675415 H 0 -1.810318 -4.531509 2.355881 H 0 -0.150757 -2.015762 4.334671 H 0 -1.535950 -2.878036 3.712433 H 0 1.001328 -2.175995 2.160843 H 0 0.647476 -3.729446 2.886398 H 0 -0.512924 -2.506409 -2.813019 H 0 2.122726 -2.135223 0.558487 H 0 2.804672 5.005402 -0.345200 H 0 3.600494 1.313980 -2.410873 H 0 4.047409 -2.085541 -0.948441 H 0 1.416107 -2.397491 -4.334656

H 0 4.232559 3.669525 -1.884094 H 0 3.728745 -2.199097 -3.418700 C 0 -2.293060 -0.420044 -1.116531 C 0 -2.529404 0.980103 -1.003647 C 0 -1.589890 1.923630 -1.370819 H 0 -3.174835 -1.053574 -1.007706 H 0 -1.686584 -0.700790 -1.978424 H 0 -3.374771 1.309555 -0.397919 H 0 -0.853943 1.673187 -2.128021 H 0 -1.789917 2.984116 -1.245056 B3LYP/6-31G* Energy = -1110.152394 B3LYP/6-31G* Free Energy = -1110.205105 B3LYP/6-31G* Free energy in solution = -1110.675111 Number of Imaginary Frequencies = 1 (-350.9) TS-2+4-SiAnti-CB B3LYP/6-31G* Geometry O 0 -0.244370 0.153778 -0.526489 C 0 -0.244370 1.455185 -0.526489 B 0 -1.320709 -0.928818 -0.526489 C 0 1.039383 2.058136 -0.028549 C 0 -0.992172 2.221893 -1.605316 C 0 -2.357727 -0.876785 -1.785797 C 0 -0.445389 -2.343063 -0.372009 C 0 1.410873 3.378113 -0.330490 C 0 1.907761 1.282059 0.758820 C 0 -3.576340 -1.843948 -1.687820 C 0 -1.639297 -0.983902 -3.162400 C 0 -0.806717 -3.527130 -1.335373 C 0 -0.131653 -2.816940 1.040787 C 0 3.107407 1.809387 1.226303 C 0 2.616394 3.903625 0.136017 C 0 -3.400940 -3.157196 -0.903427 C 0 -2.250046 -4.104538 -1.277466 C 0 -1.312759 -2.394547 -3.668427 C 0 -0.372086 -3.232620 -2.796066 C 0 -1.025711 -3.548508 1.843964 C 0 1.130829 -2.539902 1.597504 C 0 3.468994 3.123383 0.916214 C 0 1.480300 -2.947144 2.886002 C 0 -0.681671 -3.965637 3.131165 C 0 0.572128 -3.664627 3.664398 H 0 -1.958023 1.772339 -1.816711 H 0 -0.396210 2.199860 -2.527481 H 0 -1.149124 3.265442 -1.327377 H 0 -2.815689 0.121735 -1.793488 H 0 0.529984 -2.013077 -0.753967 H 0 0.770523 4.007141 -0.938858 H 0 1.627197 0.263626 1.000931 H 0 -3.943466 -2.071960 -2.699020 H 0 -4.406555 -1.310181 -1.203003 H 0 -2.273514 -0.507767 -3.926529 H 0 -0.709991 -0.396774 -3.134918 H 0 -0.149033 -4.352097 -1.025208 H 0 3.764359 1.192566 1.833572 H 0 2.887177 4.925751 -0.114273 H 0 -4.339996 -3.724380 -0.981247 H 0 -3.306335 -2.910828 0.159836 H 0 -2.271347 -4.925735 -0.548920 H 0 -2.469604 -4.578140 -2.244644 H 0 -2.247955 -2.947510 -3.825607

S42

H 0 -0.860703 -2.304626 -4.666504 H 0 0.621613 -2.761398 -2.778580 H 0 -0.234634 -4.200211 -3.300385 H 0 -2.009247 -3.801910 1.464081 H 0 1.862457 -2.007736 0.993073 H 0 4.406570 3.534256 1.280502 H 0 2.468704 -2.713577 3.275192 H 0 -1.400864 -4.531326 3.719040 H 0 0.838638 -3.990128 4.666504 C 0 -2.167800 -0.468292 1.006302 C 0 -2.435944 0.929932 0.924713 C 0 -1.484756 1.890488 1.212570 H 0 -3.056000 -1.100006 1.009171 H 0 -1.472397 -0.747681 1.797729 H 0 -3.341019 1.247635 0.404480 H 0 -0.687088 1.651260 1.908218 H 0 -1.716965 2.947418 1.113495 B3LYP/6-31G* Energy = -1110.150009 B3LYP/6-31G* Free Energy = -1110.202732 B3LYP/6-31G* Free energy in solution = -1110.673463 Number of Imaginary Frequencies = 1 (-353.4) TS-2+4-SiAnti-BC B3LYP/6-31G* Geometry O 0 -0.249313 0.233582 -0.691467 C 0 -0.249313 1.533966 -0.691467 B 0 -1.317978 -0.853210 -0.691467 C 0 1.030472 2.131332 -0.179047 C 0 -0.988907 2.292145 -1.780655 C 0 -2.378600 -0.812057 -1.939728 C 0 -0.436615 -2.258224 -0.513962 C 0 1.377136 3.471237 -0.415054 C 0 1.917847 1.328888 0.559998 C 0 -3.561600 -1.814926 -1.828827 C 0 -1.700455 -0.896103 -3.342422 C 0 -0.773117 -3.433182 -1.497894 C 0 -0.184082 -2.777374 0.897034 C 0 3.112259 1.852295 1.045578 C 0 2.576569 3.992615 0.070694 C 0 -3.294479 -3.266006 -2.240494 C 0 -2.209534 -4.007660 -1.453339 C 0 -0.362213 -1.653519 -3.428726 C 0 -0.311386 -3.118576 -2.952637 C 0 -1.190231 -3.267014 1.751160 C 0 1.132370 -2.811462 1.392502 C 0 3.448242 3.187057 0.803177 C 0 1.434967 -3.303589 2.663345 C 0 -0.895905 -3.767792 3.020264 C 0 0.419327 -3.789719 3.486252 H 0 -1.152649 3.337646 -1.514328 H 0 -1.951584 1.834885 -1.994293 H 0 -0.383652 2.264648 -2.696686 H 0 -2.881958 0.165924 -1.906998 H 0 0.558426 -1.933000 -0.846542 H 0 0.719300 4.119888 -0.983307 H 0 1.658188 0.292770 0.747100 H 0 -4.381165 -1.446167 -2.464706 H 0 -3.965897 -1.807938 -0.806381 H 0 -2.408295 -1.317413 -4.071136 H 0 -1.499039 0.123627 -3.698868 H 0 -0.139221 -4.268326 -1.167343

H 0 3.784943 1.215881 1.614151 H 0 2.828003 5.031204 -0.126389 H 0 -4.234238 -3.828308 -2.143051 H 0 -3.049713 -3.299149 -3.309952 H 0 -2.528229 -4.122757 -0.410675 H 0 -2.159790 -5.031189 -1.853485 H 0 0.389100 -1.080276 -2.871811 H 0 -0.025970 -1.633896 -4.475525 H 0 0.735443 -3.437408 -3.052292 H 0 -0.875092 -3.752136 -3.651398 H 0 -2.226730 -3.245605 1.430435 H 0 1.940094 -2.452026 0.757523 H 0 4.381180 3.594727 1.182678 H 0 2.467087 -3.311890 3.006256 H 0 -1.702179 -4.138443 3.648956 H 0 0.647415 -4.177719 4.475540 C 0 -2.168106 -0.384354 0.838409 C 0 -2.453339 1.008911 0.745789 C 0 -1.510071 1.977798 1.032196 H 0 -3.044586 -1.033463 0.852737 H 0 -1.466339 -0.642900 1.630219 H 0 -3.359802 1.315216 0.221664 H 0 -0.715515 1.749191 1.734970 H 0 -1.747849 3.032578 0.923279 B3LYP/6-31G* Energy = -1110.15058 B3LYP/6-31G* Free Energy = -1110.203493 B3LYP/6-31G* Free energy in solution = -1110.673571 Number of Imaginary Frequencies = 1 (-351.3) TS-2+4-ReAnti-CB B3LYP/6-31G* Geometry C 0 1.365921 -3.020935 0.592056 C 0 0.169891 -2.037277 0.718613 C 0 2.300049 -2.841034 -0.617462 C 0 1.710037 -2.777130 -2.039490 B 0 0.380264 -0.538177 0.089417 C 0 -1.164017 -2.707336 0.282578 C 0 0.512650 -0.436066 -1.570404 C 0 0.525055 -1.814529 -2.332672 C 0 -1.163086 -3.415558 -1.075226 O 0 -0.797379 0.241028 0.657471 C 0 -0.848358 -2.535385 -2.287552 C 0 1.516617 0.508545 -2.233459 C 0 -1.118668 1.497208 0.743271 C 0 2.911148 0.444839 -2.055191 C 0 1.051071 1.465820 -3.157181 C 0 -2.155045 1.783905 1.793732 C 0 -1.129333 2.361923 -0.503891 C 0 3.780685 1.304352 -2.730240 C 0 1.911835 2.329910 -3.835754 C 0 -2.535873 0.765625 2.684738 C 0 -2.767227 3.042221 1.914749 C 0 3.287872 2.258698 -3.620605 C 0 -3.729858 3.275070 2.896225 C 0 -3.498856 0.999863 3.662613 C 0 -4.100327 2.255783 3.774155 H 0 0.996552 -4.056488 0.619659 H 0 2.001100 -2.925674 1.483978 H 0 0.036453 -1.859772 1.797379 H 0 2.885345 -1.930786 -0.449982 H 0 3.039825 -3.654755 -0.604843

S43

H 0 1.407608 -3.786316 -2.353378 H 0 2.542542 -2.509338 -2.703766 H 0 -1.436768 -3.458221 1.040939 H 0 -1.967026 -1.957596 0.299057 H 0 -0.464630 -0.023346 -1.859619 H 0 0.637711 -1.541489 -3.392120 H 0 -0.456818 -4.255966 -1.047409 H 0 -2.150711 -3.872726 -1.231796 H 0 -0.909561 -3.173019 -3.181595 H 0 -1.642151 -1.782425 -2.404434 H 0 3.338379 -0.296005 -1.390015 H 0 -0.016724 1.523575 -3.358902 H 0 -2.023193 2.115128 -1.092865 H 0 -0.250259 2.183838 -1.118835 H 0 -1.169373 3.425781 -0.264587 H 0 4.851578 1.219803 -2.561020 H 0 1.504288 3.053543 -4.537750 H 0 -2.074127 -0.210495 2.591522 H 0 -2.496109 3.853226 1.247437 H 0 3.965576 2.926987 -4.145050 H 0 -4.191208 4.255951 2.972382 H 0 -3.783890 0.197540 4.337891 H 0 -4.851593 2.437790 4.537766 C 0 1.706100 0.227982 1.058746 C 0 1.532654 1.642776 0.998032 C 0 0.607559 2.310715 1.778625 H 0 1.558945 -0.192886 2.055252 H 0 2.624298 -0.134537 0.600784 H 0 1.977417 2.171753 0.155350 H 0 0.309753 1.883621 2.731155 H 0 0.484177 3.386765 1.690521 B3LYP/6-31G* Energy = -1110.149939 B3LYP/6-31G* Free Energy = -1110.202306 B3LYP/6-31G* Free energy in solution = -1110.673307 Number of Imaginary Frequencies = 1 (-342.4) TS-2+4-ReAnti-BC B3LYP/6-31G* Geometry C 0 2.298828 -2.279297 1.162735 C 0 0.913925 -1.584412 1.157257 C 0 2.699432 -3.016373 -0.119171 C 0 2.788986 -2.163956 -1.389740 B 0 0.870529 -0.106827 0.452087 C 0 -0.218735 -2.539734 0.665909 C 0 1.177231 -0.051163 -1.189300 C 0 1.508545 -1.435959 -1.867218 C 0 -0.737015 -2.331436 -0.767395 O 0 -0.492706 0.446182 0.847076 C 0 0.274506 -2.384232 -1.925781 C 0 2.113083 1.013809 -1.757858 C 0 -1.059326 1.614029 0.795837 C 0 1.658859 1.847778 -2.798523 C 0 3.452774 1.186691 -1.360535 C 0 -2.241928 1.750381 1.712204 C 0 -1.090530 2.386871 -0.509979 C 0 2.473434 2.815659 -3.388458 C 0 4.276260 2.150116 -1.947006 C 0 -3.087936 2.871185 1.679688 C 0 -2.523987 0.724960 2.631454 C 0 3.791107 2.976822 -2.960861 C 0 -3.617691 0.818497 3.487793

C 0 -4.181320 2.963669 2.539917 C 0 -4.451584 1.938492 3.447174 H 0 2.317581 -3.016098 1.980515 H 0 3.082077 -1.548233 1.412430 H 0 0.692703 -1.394348 2.218887 H 0 2.000610 -3.845184 -0.290970 H 0 3.677536 -3.491730 0.042664 H 0 3.099319 -2.830582 -2.207947 H 0 3.604645 -1.438095 -1.287613 H 0 0.094345 -3.586578 0.794556 H 0 -1.087296 -2.415314 1.326600 H 0 0.197600 0.196106 -1.623016 H 0 1.723618 -1.183609 -2.915451 H 0 -1.511948 -3.085739 -0.967468 H 0 -1.257751 -1.366700 -0.802505 H 0 0.629272 -3.415817 -2.058670 H 0 -0.288467 -2.151993 -2.840790 H 0 0.641190 1.723450 -3.163788 H 0 3.872253 0.555832 -0.584915 H 0 -0.128220 2.355286 -1.015976 H 0 -1.363480 3.432495 -0.359314 H 0 -1.845703 1.933502 -1.166641 H 0 2.077194 3.438477 -4.186996 H 0 5.304840 2.250183 -1.608673 H 0 -2.899109 3.684021 0.986740 H 0 -1.880081 -0.146545 2.655914 H 0 4.432144 3.727875 -3.414749 H 0 -3.822189 0.012161 4.186981 H 0 -4.823090 3.839554 2.498688 H 0 -5.304855 2.010910 4.115982 C 0 1.896378 0.946838 1.503189 C 0 1.477539 2.297700 1.310974 C 0 0.361908 2.820908 1.936035 H 0 1.702682 0.564362 2.506973 H 0 2.916046 0.735153 1.186615 H 0 1.914612 2.852448 0.481033 H 0 0.035095 2.399490 2.881516 H 0 0.051193 3.845169 1.748077 B3LYP/6-31G* Energy = -1110.151827 B3LYP/6-31G* Free Energy = -1110.204233 B3LYP/6-31G* Free energy in solution = -1110.675127 Number of Imaginary Frequencies = 1 (-333.7) TS-2+4-SiSyn-CB B3LYP/6-31G* Geometry C 0 -2.304504 -2.507843 0.107132 C 0 -1.081482 -1.581589 0.338287 C 0 -2.328049 -3.305862 -1.201385 C 0 -2.336441 -2.487015 -2.495972 B 0 -1.157623 -0.106461 -0.367798 C 0 0.270126 -2.313492 0.072464 C 0 -1.391541 -0.118576 -2.020691 C 0 -1.163193 -1.501434 -2.741409 C 0 0.984253 -1.975800 -1.246964 C 0 -0.816742 1.023041 -2.842407 C 0 0.219849 -2.195648 -2.562698 C 0 0.524338 1.074997 -3.264908 C 0 -1.652206 2.077728 -3.256073 C 0 -1.175781 3.141678 -4.024948 C 0 1.004639 2.128555 -4.044052 C 0 0.160919 3.174042 -4.423996

S44

O 0 0.000458 0.669357 0.230072 C 0 0.358246 1.868912 0.574280 C 0 1.209946 1.913727 1.812790 C 0 0.602844 2.926468 -0.483932 C 0 1.304900 0.771606 2.627457 C 0 1.931702 3.060257 2.184616 C 0 2.721283 3.064148 3.334229 C 0 2.092697 0.777863 3.774902 C 0 2.805069 1.924683 4.134796 H 0 -2.349045 -3.237961 0.929626 H 0 -3.233322 -1.923508 0.184891 H 0 -1.096268 -1.372467 1.419907 H 0 -3.218414 -3.950700 -1.199539 H 0 -1.473358 -3.994308 -1.218704 H 0 -2.346695 -3.199127 -3.334061 H 0 -3.282547 -1.930023 -2.568222 H 0 0.133392 -3.402161 0.150650 H 0 0.971924 -2.052612 0.875977 H 0 -2.477875 0.016541 -2.114197 H 0 -1.237839 -1.269821 -3.813507 H 0 1.301849 -0.927567 -1.193848 H 0 1.913345 -2.562057 -1.298508 H 0 0.085800 -3.274338 -2.726669 H 0 0.882690 -1.869629 -3.374969 H 0 1.209381 0.285049 -2.978470 H 0 -2.704758 2.054749 -2.979080 H 0 -1.854706 3.936996 -4.323944 H 0 2.046844 2.131607 -4.355225 H 0 0.536545 3.994293 -5.029968 H 0 -0.167709 2.906113 -1.250122 H 0 1.564774 2.722046 -0.969925 H 0 0.645950 3.928452 -0.053543 H 0 0.758881 -0.120544 2.343414 H 0 1.887726 3.959412 1.580200 H 0 3.273500 3.961014 3.601532 H 0 2.154877 -0.117020 4.388275 H 0 3.420914 1.928925 5.029984 C 0 -2.572433 0.728027 0.428253 C 0 -2.305420 2.127945 0.488159 C 0 -1.489319 2.682343 1.452530 H 0 -2.627502 0.254654 1.410675 H 0 -3.420914 0.447372 -0.196747 H 0 -2.563751 2.737854 -0.378372 H 0 -1.359894 2.167389 2.399400 H 0 -1.287674 3.749329 1.465927 B3LYP/6-31G* Energy = -1110.146875 B3LYP/6-31G* Free Energy = -1110.199542 B3LYP/6-31G* Free energy in solution = -1110.670958 Number of Imaginary Frequencies = 1 (-337.0) TS-2+4-SiSyn-BC B3LYP/6-31G* Geometry C 0 -2.314606 -3.741013 -0.187378 C 0 -2.051254 -2.274353 0.265518 C 0 -1.141907 -4.515167 -0.820221 C 0 0.194290 -4.602127 -0.061981 B 0 -0.918289 -1.456818 -0.585327 C 0 -1.867538 -2.170547 1.805435 C 0 0.640366 -2.036957 -0.479065 C 0 0.845306 -3.291214 0.465469 C 0 -0.890594 -3.160477 2.448837

O 0 -1.161926 0.001373 -0.250763 C 0 1.750900 -1.039948 -0.171417 C 0 0.563600 -3.081300 1.972870 C 0 -1.043350 1.174728 -0.800674 C 0 2.904953 -1.007889 -0.973816 C 0 1.721039 -0.170944 0.934921 C 0 -2.013977 2.189407 -0.263794 C 0 0.308136 1.685608 -1.269257 C 0 2.792740 0.673370 1.229538 C 0 3.974594 -0.154419 -0.695267 C 0 -3.103806 1.763214 0.515228 C 0 -1.863007 3.564377 -0.507980 C 0 3.926559 0.689590 0.414612 C 0 -2.776184 4.483765 0.007751 C 0 -4.014404 2.682663 1.028015 C 0 -3.856186 4.047852 0.775894 H 0 -2.717682 -4.320007 0.656097 H 0 -3.119186 -3.741928 -0.935898 H 0 -2.988358 -1.728897 0.067078 H 0 -0.939224 -4.092697 -1.810471 H 0 -1.478897 -5.543320 -1.017365 H 0 0.090912 -5.296021 0.783966 H 0 0.904785 -5.086716 -0.746414 H 0 -2.847870 -2.326660 2.283188 H 0 -1.571243 -1.144012 2.066391 H 0 0.888046 -2.432129 -1.476135 H 0 1.928177 -3.478836 0.424500 H 0 -0.902039 -3.004211 3.537140 H 0 -1.264313 -4.182388 2.301147 H 0 1.127365 -3.858139 2.510391 H 0 1.003387 -2.132538 2.297531 H 0 2.966141 -1.672012 -1.834183 H 0 0.835602 -0.134079 1.560898 H 0 0.201400 2.475983 -2.014862 H 0 0.907791 0.881058 -1.689224 H 0 0.857132 2.092500 -0.413025 H 0 2.736923 1.326965 2.097153 H 0 4.848358 -0.156067 -1.342743 H 0 -3.219910 0.704865 0.719086 H 0 -1.031067 3.930252 -1.099900 H 0 4.759033 1.350494 0.641586 H 0 -2.639800 5.543335 -0.190933 H 0 -4.848343 2.333038 1.630737 H 0 -4.567032 4.765106 1.177048 C 0 -1.511139 -1.510132 -2.333893 C 0 -1.257187 -0.269821 -2.987061 C 0 -1.992722 0.869843 -2.731659 H 0 -2.574570 -1.713745 -2.196045 H 0 -0.994812 -2.359909 -2.777313 H 0 -0.321671 -0.158371 -3.537125 H 0 -2.998032 0.776932 -2.331879 H 0 -1.777924 1.800430 -3.248489 B3LYP/6-31G* Energy = -1110.145328 B3LYP/6-31G* Free Energy = -1110.19829 B3LYP/6-31G* Free energy in solution = -1110.669345 Number of Imaginary Frequencies = 1 (-349.8) Product P-2+4-R (Global minimum)

B3LYP/6-31G* Geometry O 0 0.377533 0.069992 -0.786865 C 0 0.377533 1.518646 -0.786865

S45

B 0 -0.654205 -0.825439 -0.786865 C 0 -0.292557 2.064117 0.479645 C 0 -2.201111 -0.454117 -0.702026 C 0 -0.145721 -2.341476 -0.946121 C 0 1.887741 1.902710 -0.736267 C 0 -0.246414 2.023651 -2.093658 C 0 -2.882919 -1.104218 0.539978 C 0 -2.946533 -0.781906 -2.033981 C 0 -1.263123 -3.427338 -1.054916 C 0 -0.031158 1.451294 1.715652 C 0 0.948380 -2.733307 0.040710 C 0 2.704865 1.382523 -1.886490 C 0 -1.107712 3.202911 0.465118 C 0 -3.274170 -2.583008 0.427826 C 0 -2.136948 -3.589798 0.211090 C 0 -2.308533 -1.859314 -2.932892 C 0 -2.105255 -3.276276 -2.358170 C 0 0.877731 -2.422500 1.408783 C 0 2.071000 -3.451248 -0.400040 C 0 -1.656845 3.707855 1.646637 C 0 -0.580124 1.952377 2.895035 C 0 3.423737 2.142410 -2.714386 C 0 3.079041 -3.844482 0.481125 C 0 1.880814 -2.814209 2.297302 C 0 -1.397675 3.084290 2.865921 C 0 2.987976 -3.528076 1.837296 H 0 -2.298660 0.624527 -0.538956 H 0 0.349640 -2.332306 -1.932159 H 0 2.288559 1.500000 0.202972 H 0 1.964539 2.994995 -0.675934 H 0 -1.324478 1.847031 -2.126953 H 0 0.221527 1.509583 -2.936859 H 0 -0.067520 3.095673 -2.224747 H 0 -3.801437 -0.536804 0.749115 H 0 -2.247040 -0.960434 1.426132 H 0 -3.990952 -1.048035 -1.820267 H 0 -2.998169 0.134628 -2.636566 H 0 -0.733795 -4.386078 -1.149658 H 0 0.604507 0.571579 1.750885 H 0 2.698471 0.301163 -2.014191 H 0 -1.327179 3.706329 -0.470734 H 0 -4.014847 -2.697815 -0.373900 H 0 -3.803070 -2.863144 1.349579 H 0 -1.483856 -3.602753 1.092865 H 0 -2.591141 -4.590103 0.168198 H 0 -1.337463 -1.481720 -3.285492 H 0 -2.922089 -1.954605 -3.839508 H 0 -1.618057 -3.862228 -3.149368 H 0 -3.084671 -3.750259 -2.205841 H 0 0.027557 -1.860977 1.787994 H 0 2.155731 -3.703232 -1.455322 H 0 -2.290558 4.590118 1.608139 H 0 -0.366745 1.458420 3.839508 H 0 3.457916 3.225967 -2.614761 H 0 4.014862 1.712097 -3.518677 H 0 3.937790 -4.396042 0.106247 H 0 1.796371 -2.558212 3.350708 H 0 -1.826492 3.475418 3.784546 H 0 3.771545 -3.831085 2.526672 B3LYP/6-31G* Energy = -1110.212861 B3LYP/6-31G* Free Energy = -1110.269111 B3LYP/6-31G* Free energy in solution = -1110.732472

Number of Imaginary Frequencies = 0 Product P-2+4-R (from IRC of TS-2+4-ReSyn-CB)

B3LYP/6-31G* Geometry O 0 -0.340530 0.170715 0.130814 C 0 -0.340530 1.606262 0.130814 B 0 -1.268555 -0.828323 0.130814 C 0 1.056519 2.050812 0.610123 C 0 -2.847214 -0.684387 0.324402 C 0 -0.650314 -2.298660 -0.087021 C 0 -1.398560 2.196457 1.080170 C 0 -0.511368 2.077560 -1.346344 C 0 -3.701431 -1.507385 -0.687271 C 0 -3.188736 -0.999161 1.816040 C 0 -1.488144 -3.485733 0.502289 C 0 0.840027 -2.414566 0.189056 C 0 1.375000 3.416809 0.680008 C 0 2.037384 1.122940 0.975998 C 0 -1.794968 1.697281 -2.028137 C 0 -3.908539 -3.000351 -0.401184 C 0 -2.657471 -3.884354 -0.429825 C 0 -2.185516 -1.916855 2.542648 C 0 -1.957672 -3.334091 1.983719 C 0 1.357025 -2.631653 1.477127 C 0 1.761871 -2.307556 -0.864731 C 0 2.633057 3.842331 1.103958 C 0 3.297348 1.549072 1.403473 C 0 -1.870087 0.917252 -3.109024 C 0 3.136292 -2.406509 -0.648651 C 0 2.731598 -2.736404 1.700241 C 0 3.602921 2.907242 1.470000 C 0 3.630524 -2.623688 0.638657 H 0 -3.143539 0.351608 0.141953 H 0 -0.748444 -2.405472 -1.182465 H 0 -1.293808 1.746658 2.072464 H 0 -2.418686 2.035477 0.729340 H 0 -1.248459 3.274170 1.187820 H 0 0.337067 1.676422 -1.911453 H 0 -0.409225 3.170654 -1.355774 H 0 -4.700150 -1.048096 -0.724289 H 0 -3.283676 -1.384338 -1.696487 H 0 -4.201904 -1.416107 1.895462 H 0 -3.213959 -0.053787 2.372986 H 0 -0.815704 -4.353668 0.486862 H 0 0.639389 4.167664 0.401855 H 0 1.816300 0.065720 0.924347 H 0 -2.714478 2.118668 -1.621155 H 0 -4.409195 -3.114868 0.568832 H 0 -4.620529 -3.392944 -1.140442 H 0 -2.277130 -3.944122 -1.459946 H 0 -2.965561 -4.905930 -0.164688 H 0 -2.506302 -2.019730 3.588623 H 0 -1.216370 -1.396667 2.590500 H 0 -1.218323 -3.814545 2.637329 H 0 -2.877060 -3.921127 2.116943 H 0 0.682114 -2.717087 2.322815 H 0 1.392334 -2.142822 -1.874786 H 0 2.853302 4.905914 1.148056 H 0 4.039474 0.805206 1.681183 H 0 -2.818832 0.692017 -3.588638 H 0 -0.980316 0.484497 -3.562134 H 0 3.821106 -2.318863 -1.488571

S46

H 0 3.098770 -2.907104 2.709442 H 0 4.584290 3.236298 1.801666 H 0 4.700165 -2.709106 0.811157 B3LYP/6-31G* Energy = -1110.205854 B3LYP/6-31G* Free Energy = -1110.261397 B3LYP/6-31G* Free energy in solution = -1110.727965 Number of Imaginary Frequencies = 0 Product P-2+4-S (Global minimum)

B3LYP/6-31G* Geometry O 0 0.491852 -0.235733 0.080322 C 0 0.491852 1.212296 0.080322 B 0 -0.537643 -1.133057 0.080322 C 0 -0.231216 1.757935 -1.155762 C 0 -2.084747 -0.765259 -0.016495 C 0 -0.020615 -2.652924 0.146378 C 0 -0.071289 1.706696 1.417923 C 0 2.011169 1.555710 -0.003113 C 0 -2.858337 -1.226242 1.257034 C 0 -2.735474 -1.290039 -1.335938 C 0 -1.132614 -3.749603 0.132172 C 0 -1.053314 2.890869 -1.105881 C 0 -0.019104 1.148224 -2.402756 C 0 1.014313 -2.908340 1.236893 C 0 2.336807 3.022476 -0.043625 C 0 -3.237488 -2.710205 1.337402 C 0 -2.083176 -3.721252 1.353043 C 0 -2.049606 -2.487823 -2.019089 C 0 -1.890503 -3.801514 -1.228058 C 0 0.898926 -2.372452 2.529541 C 0 2.120331 -3.732391 0.976212 C 0 -0.618912 1.646942 -3.558182 C 0 -1.654572 3.393692 -2.262802 C 0 3.077011 3.661407 0.864304 C 0 3.069200 -4.014175 1.959259 C 0 1.842621 -2.651184 3.519669 C 0 -1.441803 2.773788 -3.493134 C 0 2.933548 -3.474670 3.239349 H 0 -2.189743 0.324722 -0.040665 H 0 0.527237 -2.778366 -0.803619 H 0 0.120453 2.774460 1.555939 H 0 0.434738 1.170959 2.227112 H 0 -1.146423 1.528107 1.503403 H 0 2.397766 1.065659 -0.906509 H 0 2.502472 1.078018 0.852188 H 0 -3.790146 -0.644455 1.312790 H 0 -2.288284 -0.951400 2.158218 H 0 -3.794785 -1.522461 -1.158218 H 0 -2.730179 -0.470490 -2.064468 H 0 -0.602188 -4.708420 0.217438 H 0 -1.234924 3.390533 -0.160034 H 0 0.616425 0.269669 -2.464691 H 0 1.939163 3.581604 -0.890700 H 0 -3.830856 -2.859344 2.250320 H 0 -3.916794 -2.949860 0.509384 H 0 -1.486130 -3.583496 2.263962 H 0 -2.529617 -4.721878 1.442871 H 0 -2.606644 -2.720337 -2.937576 H 0 -1.057343 -2.163086 -2.364441 H 0 -1.356720 -4.497528 -1.889465 H 0 -2.879562 -4.252609 -1.068405

H 0 0.062744 -1.719238 2.767395 H 0 2.239105 -4.157745 -0.018478 H 0 -0.442520 1.154617 -4.511063 H 0 -2.292007 4.271515 -2.196579 H 0 3.499054 3.145477 1.724640 H 0 3.299133 4.721893 0.777847 H 0 3.916794 -4.653122 1.723450 H 0 1.725311 -2.220261 4.511047 H 0 -1.910690 3.163223 -4.392639 H 0 3.670990 -3.690353 4.007996 B3LYP/6-31G* Energy = -1110.212507 B3LYP/6-31G* Free Energy = -1110.268871 B3LYP/6-31G* Free energy in solution = -1110.733084 Number of Imaginary Frequencies = 0 Product P-2+4-S (from IRC of TS-2+4-SiAnti-BC)

B3LYP/6-31G* Geometry O 0 -0.347975 0.222014 -0.478260 C 0 -0.347975 1.654271 -0.478260 B 0 -1.249757 -0.800830 -0.478260 C 0 1.020438 2.081388 -1.051714 C 0 -1.473720 2.218372 -1.362445 C 0 -2.838700 -0.691030 -0.389308 C 0 -0.518444 -2.220097 -0.692896 C 0 -0.412165 2.156004 0.996057 C 0 1.304138 3.437698 -1.275033 C 0 2.020079 1.141979 -1.331432 C 0 -3.438671 -1.539886 0.772270 C 0 -3.493784 -1.016849 -1.770002 C 0 -1.450901 -3.450241 -0.923496 C 0 0.578195 -2.520273 0.323491 C 0 -1.664465 1.850329 1.768226 C 0 3.259470 1.546110 -1.832934 C 0 2.541738 3.842310 -1.774348 C 0 -3.600079 -3.046398 0.538898 C 0 -2.314628 -3.845726 0.295753 C 0 -2.678770 -1.916513 -2.719922 C 0 -2.274707 -3.326997 -2.240746 C 0 0.451127 -2.211796 1.687228 C 0 1.761353 -3.155071 -0.088454 C 0 -1.695241 1.147769 2.902921 C 0 3.526609 2.895456 -2.059647 C 0 2.772586 -3.474281 0.818323 C 0 1.457464 -2.530473 2.600940 C 0 2.623611 -3.164579 2.171107 H 0 -1.377561 3.302620 -1.466531 H 0 -2.464487 2.009790 -0.956394 H 0 -1.408301 1.780181 -2.363420 H 0 -3.117020 0.337093 -0.140442 H 0 0.010783 -2.076241 -1.650575 H 0 0.454365 1.734709 1.517618 H 0 -0.265399 3.244485 0.969433 H 0 0.557401 4.197054 -1.057570 H 0 1.826716 0.092736 -1.146585 H 0 -4.437965 -1.135413 0.991984 H 0 -2.850158 -1.373371 1.685547 H 0 -4.491397 -1.450667 -1.614682 H 0 -3.664448 -0.072141 -2.302997 H 0 -0.775886 -4.305113 -1.072317 H 0 -2.594748 2.271608 1.386702 H 0 4.019043 0.797450 -2.043529

S47

H 0 2.734257 4.899223 -1.939991 H 0 -4.104716 -3.472068 1.417541 H 0 -4.292741 -3.209193 -0.297134 H 0 -1.688830 -3.817243 1.197182 H 0 -2.602085 -4.899223 0.168056 H 0 -1.768301 -1.372982 -3.012829 H 0 -3.250021 -2.035204 -3.651103 H 0 -1.684467 -3.768880 -3.054981 H 0 -3.173332 -3.953900 -2.159418 H 0 -0.442567 -1.703926 2.040988 H 0 1.889057 -3.402777 -1.140628 H 0 -2.619504 0.981493 3.449810 H 0 -0.790547 0.723117 3.333476 H 0 4.491397 3.207942 -2.450366 H 0 3.678029 -3.963095 0.466905 H 0 1.329897 -2.278826 3.651103 H 0 3.408956 -3.410320 2.881047 B3LYP/6-31G* Energy = -1110.207009 B3LYP/6-31G* Free Energy = -1110.263295 B3LYP/6-31G* Free energy in solution = -1110.727903 Number of Imaginary Frequencies = 0

asymmetric allylboration reactions with …

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