asymmetric catalytic enantio- and diastereoselective boron ...€¦ · jian-bo xie*, siqi lin, shuo...

S1

Supporting Information

for

Asymmetric Catalytic Enantio- and Diastereoselective

Boron Conjugate Addition Reactions of

-Functionalized ,-Unsaturated Carbonyl Substrates

Jian-Bo Xie*, Siqi Lin, Shuo Qiao, Guigen Li

*Corresponding author. E-mail: [email protected]

Contents

General Information S2

Supplementary Schemes and Table S3

Preparation of L3 S4

Synthesis and Characterization of Products (includes NMR spectra) S5-S52

A. Preparation of racemic products S5

B. Preparation of optical products S6

C. Characterization of products S7-S51

D. Equilibrium experiment with (R,R)-2a S51-S52

HPLC Traces S53-S81

X-ray data for (S,R)-2k, anti S82-S91

S2

Materials and Methods

General Information

All commercially available chemicals including solvents, unless otherwise mentioned, were used

without purification. The boron conjugate addition reactions were all done under argon

atmosphere. Molecular sieve (4 Å) was dried over 300 ºC under vacuum. Toluene was distilled

from Na/benzophenone and kept with 4 Å molecular sieve. MeOH, EtOH, BnOH, nPrOH,

iPrOH,

tBuOH, CF3CH2OH and (CF3)2CHOH were dried over 4 Å molecular sieve. B2Pin2 was purchased

from Frontier Scientific. CuCl (anhydrous, beads, ≥ 99.99% trace metals basis), silver

bis(trifluoromethanesulfonyl)imide (AgNTf2), (S)-L7, (S,R,R)-L8 and (R,R,R)-L9 were purchased

from Sigma-Aldrich. 4 Å molecular sieve (powder), (S)-(R)-ppfa (L1), its enantiomer and

(S)-(R)-L2 were purchased from Alfa Aesar. (S)-(R)-L3 was synthesized from (S)-(R)-L2 with

benzaldehyde and NaBH(OAc)3. Josiphos (S)-(R)-L4 was purchased from Strem Chemicals Inc.

(S)-(S)-L5 and (S,S)-L6 were purchased from TCI. (R,R)-L10 was synthesized following

procedures described in the literature11

. All the -substituted ,-unsaturated carbonyl

compounds were prepared following the procedures described in the literature. The NMR spectra

were recorded at 400, 100 and 162 MHz for 1H,

13C and

31P respectively with a JEOL ECS 400

MHz Spectrometer. Optical rotations were determined using an Autopol® IV automatic

polarimeter. HPLC analyses were performed using a Waters Delta 600 instrument with a Waters

2996 PDA detector. X-ray diffraction data was collected on a Bruker PLATFORM three circle

diffractometer equipped with an APEX II CCD detector and operated at 1500 W (50kV, 30 mA) to

generate (graphite monochromated) Mo Kα radiation (λ = 0.71073 Å). All the glasswares used

were dried overnight at 110 oC. The NMR spectra were recorded at 400, 100, and 162 MHz for

1H,

13C, and

31P, respectively with a JEOL ECS 400 MHz Spectrometer. Optical rotations were

determined using an Autopol® IV automatic polarimeter.

1 L.-L Wu et al., Synthesis of 3-fluoro-3-aryl oxindoles: direct enantioselective α arylation of amides. Angew.

Chem. Int. Ed. 51, 2870 (2012).

S3

Supplementary Schemes and Table

Scheme S1. Screening the Chiral Ligands

Scheme S2. Synthesis of 1,3-Diols

Table S1. Influence of Bulk and pKa of the Additives

entry additive (pKa) conv

(%)

dr

(syn/anti) ee (%, syn/anti)

2n

1 MeOH (15.54) 40 5:1 87/87

2 tBuOH (17.0) 71 12:1 80/-

3 TFE (12.5) 98 3.1:1 94/93

4 HFIP (9.3) 99 1:1.4 93/83

4b

5 MeOH >99 1.9:1 89/89

6 iPrOH (16.5) >99 2.1:1 85/90

7 BnOH (15.0) >99 1.2:1 91/91

8 tBuOH >99 3:1 98/92

9 TFE >99 1:1.3 85/94

10 HFIP >99 1:1.7 84/93

11 PhOH (9.95) >99 1.5:1 87/88

12 C6F5OH (4.46) >99 1:1.4 89/88

S4

Preparation of L3

(S)-(R)-L2 (200 mg, 0.468 mmol) and 4 Å molecular sieve (200 mg) were added to a dry 10 mL

Schlenk tube and then purged with argon. Benzaldehyde (99 mg, 0.933 mmol) and

1,2-dichloroethane (DCE, 3 mL) were added to the tube by syringe. The mixture was stirred for 30

minutes. NaBH(OAc)3 (397 mg, 1.873 mmol) and AcOH (42 mg, 0.699 mmol) were added then.

The reaction mixture was stired overnight before it was diluted by dichloromethane (DCM). The

organic layer was washed by saturated Na2CO3 and brine successively and dried by Na2SO4. After

evaporation of the volatile under vacuum, the residue was purified through silica gel

chromatography. DCM was used as eluent. The yellow sticky foam product was obtained as a

mixture of diastereoisomers (4.9:1 dr). 1H NMR (major, 400 MHz, CDCl3) δ 1.44 (CH3, d, J = 6.9

Hz, 3H), 3.94 (NCH3, s, 3H), 3.98 (NCH, m, 1H), 4.49 (PhCH2, m, 2H), 6.60–7.70 (Ar-H, m,

18H). 31

P NMR (162 MHz, CDCl3) δ -22.8 (major), -23.2 (minor). HRMS (ESI) m/z calcd for

C32H33FeNP ([M + H]+): 518.1695; found: 518.1688. [α]

25

D +348.3 (c 1.80, CH2Cl2).

S5

Synthesis and Characterization of Products

A) Preparation of Racemic Products

For (rac)-2a-r:

CuCl (6 mg, 0.06 mmol), NaOtBu (5.8 mg, 0.06 mmol), bis(pinacolato)diboron (B2pin2, 152 mg,

0.6 mmol) and relative -substituted ,-unsaturated compounds (1a-r, 0.3 mmol) were added

into a dry 10 mL Schlenk tube and then purged with argon. Anhydrous toluene (2 mL), THF (2

mL) and MeOH (0.2 mL) were added successively by syringe. The reaction mixture was stirred

for 24 hours before filtration through celite and wash with hexanes. The filtrate was concentrated

and the residue was analyzed with a 1H NMR spectrum to record the relative δ shifts of the

characteristic protons and then determine the dr (diastereomeric ratio) value. The mixture was then

purified by flash chromatography (ethyl acetate/hexanes = 1:10 to 1:25) to afford the product

(sometimes the diastereoisomers could be separated). The racemic sample (pure diastereoisomer

or the mixture) was subjected to chiral HPLC analysis (chiral columns: AD, AS-H, OD-H).

For (rac)-4a-d and 6:

The procedure was almost same as the one for (rac)-2a-r except ICyCuO

tBu was used intead of

CuCl/NaOtBu and THF was excluded. The anti-4 and 6 are unstable in the presence of NaO

tBu.

For (rac)-8 and (rac)-9:

CuCl (3.0 mg, 0.03 mmol) and (rac)-L1 (15.7 mg, 0.036 mmol) were added to a dry 10 mL

Schlenk tube and then purged with argon. Anhydrous toluene (2 mL) was added and the mixture

was stirred for 24 hours. Into a another dry 10 mL Schlenk tube was added AgNTf2 (12.0 mg, 0.03

mmol) and 4 Å molecular sieve (~ 100 mg). The tube was purged with argon and the Cu(L1)Cl

solution was added. The mixture was stirred for 40 minutes. The solution of 7 (27 mg, 0.15 mmol)

and B2pin2 (152 mg, 0.6 mmol) in toluene (1 mL) was added, followed by the addition of

CF3CH2OH (0.10 mL). The reaction mixture was stirred vigorously for 48 hours. After filtration

S6

through celite and wash with hexanes, the filtrate was concentrated and the residue was analyzed

with a 1H NMR spectrum to record the relative δ shifts of the characteristic protons and then

determine the dr (diastereomeric ratio) value. The crude product was then redissolved in

anhydrous THF (2 mL). iPrOH (0.2 mL) and mCPBA (~77%, 155 mg, ~0.9 mmol) were then

added and the reaction mixture was stirred for 20 minutes. The mixture was concentrated under

vacuum and redissolved in ethyl acetate. The organic layer was washed with saturated NaHCO3

for three times and the water layer was extracted with ethyl acetate. The combined organic layer

was washed with brine and dried over Na2SO4. The crude product was concentrated and purified

through flash chromatography.

B) Preparation of Optical Products

General produre (5 mol% catalyst): CuCl (7.6 mg, 0.0768 mmol) and (S)-(R)-L1 (67.8 mg, 0.1535

mmol) were added to a dry 10 mL Schlenk tube and then purged with argon. Anhydrous toluene

(8.0 mL) was added and the mixture was stirred for 24 hours. The catalyst solution (~0.0096 M)

was obtained then. Into a another dry 10 mL Schlenk tube was added AgNTf2 (3.8 mg, 0.0098

mmol) and 4 Å molecular sieve (~ 70 mg). The tube was purged with argon. 1.0 mL of the catalyst

solution and 1 mL anhydrous toluene was added. The mixture was stirred for 40 minutes. The

solution of substrate (0.192 mmol) and B2pin2 (194 mg, 0.768 mmol) in toluene (0.5 mL) was

added, followed by the addition of alcohols (0.97 mmol, 5 eq). Then the reaction was stirred

vigorously for 48 hours. After filtration through celite and wash with hexanes, the filtrate was

concentrated and the residue was analyzed with a 1H NMR spectrum to record the relative δ shifts

of the characteristic protons and then determine the dr (diastereomeric ratio) value. The mixture

was then purified by flash chromatography (ethyl acetate/hexanes = 1:10 to 1:25, the dr of

products would be slightly decreased due to isomerization on silica gel) to afford the product

(sometimes the diastereoisomers could be separated). The optical sample (pure diastereoisomer or

the mixture) was subjected to chiral HPLC analysis (chiral columns: AD, AS-H, OD-H).

S7

C) Characterization of Products

(3R,4R)-3-Methyl-4-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-2-one

[(R,R)-2a, syn]

Colorless oil, 99%, 92% ee, 24:1 dr. 1H NMR (syn, 400 MHz, CDCl3) δ 1.16 (CH3, d, J = 6.9 Hz, 3H), 1.16 (CH3, s, 6H), 1.20 (CH3, s,

6H), 1.85 (COCH3, s, 3H), 2.57 (BCH, d, J = 10.5 Hz, 1H), 3.09 (CH, qd, J = 10.5 Hz, J = 6.9 Hz,

1H), 7.08–7.12 (Ar-H, m, 1H), 7.17–7.23 (Ar-H, m, 4H). 13

C NMR (syn, 100 MHz, CDCl3) δ 16.7,

24.6, 24.7, 29.1, 29.8, 50.0, 83.6, 125.8, 128.5, 129.0, 140.5, 212.9. HRMS (ESI) m/z calcd for

C17H25BNaO3 ([M + Na]+): 311.1789; found: 311.1786. [α]

25

D –38.8 (c 1.20, CH2Cl2). The

enantiomeric excess was determined by HPLC with a Chiralpak AD column: eluent,

hexanes/iPrOH (98:2); flow rate = 0.5 mL/min; tR (1, anti- isomer) = 22.0 min, tR (2, cis- isomer)

= 25.2 min, tR (3, anti- isomer) = 25.8 min, tR (4, cis- isomer) = 26.6 min.

S8

(3S,4R)-3-Methyl-4-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-2-one

[(S,R)-2a, anti]

Colorless oil. 1H NMR (anti, 400 MHz, CDCl3) δ 0.97 (CH3, d, J = 6.8 Hz, 3H), 1.09 (CH3, s, 6H), 1.17 (CH3, s,


1H), 7.11–7.25 (Ar-H, m, 5H). 13

C NMR (anti, 100 MHz, CDCl3) δ 16.3, 24.5, 24.6, 28.1, 29.8,

50.7, 83.3, 125.7, 128.5, 129.0, 140.7, 213.2. [α]25

D –20.8 (c 0.60, CH2Cl2). The enantiomeric

excess was determined by HPLC with a Chiralpak AD column: eluent, hexanes/iPrOH (99:1);

flow rate = 0.5 mL/min; tR (1, anti- isomer) = 23.5 min, tR (2, cis- isomer + anti- isomer) = 28.3

min, tR (3, cis- isomer) = 29.8 min.

S9

(3R,4R)-4-(2-Fluorophenyl)-3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-2

-one [(R,R)-2b, syn]

S10

Colorless oil, >99%, 93% ee, 33:1 dr. 1H NMR (syn, 400 MHz, CDCl3) δ 1.18 (CH3, d, J = 7.4 Hz, 3H), 1.18 (CH3, s, 6H), 1.22 (CH3, s,

6H), 1.96 (COCH3, s, 3H), 2.88(BCH, d, J = 8.7 Hz, 1H), 3.07 (CH, qd, J = 8.7 Hz, J = 7.4 Hz,

1H), 6.92–7.02 (Ar-H, m, 2H), 7.07–7.12 (Ar-H, m, 1H), 7.22–7.26 (Ar-H, m, 1H). 13

C NMR (syn,

100 MHz, CDCl3) δ 16.0, 24.5, 24.6, 28.1, 48.8, 83.5, 115.1, 115.3, 123.9, 127.3, 127.4, 127.5,

127.6, 131.2, 131.2, 159.6, 162.1, 212.2. HRMS (ESI) m/z calcd for C17H24BFNaO3 ([M + Na]+):

329.1695; found: 329.1693. [α]25

D –27.0 (c 1.10, CH2Cl2). The enantiomeric excess was

determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/iPrOH (99:1); flow rate =

0.5 mL/min; tR (1, anti- isomers mixture) = 19.3 min, tR (2, cis- isomer) = 22.7 min, tR (3, cis-

isomer) = 24.4 min.

For (S,R)-2b, the diagnostic peaks on 1H NMR are: δ 2.17 (COCH3, s, 3H), 2.63 (BCH, d, J = 11.0

Hz, 1H).

S11

(3R,4R)-4-(2-Chlorophenyl)-3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-2

-one [(R,R)-2c, syn]


6H), 1.99 (COCH3, s, 3H), 3.11 (CH, qd, J = 8.2 Hz, J = 6.9 Hz, 1H), 3.14(BCH, d, J = 8.2 Hz,

1H), 7.03–7.08 (Ar-H, m, 1H), 7.11–7.15 (Ar-H, m, 1H), 7.28–7.31 (Ar-H, m, 2H). 13

C NMR (syn,

100 MHz, CDCl3) δ 15.7, 24.7, 24.8, 27.9, 48.7, 83.6, 126.7, 127.1, 129.7, 130.9, 134.4, 138.5,

212.3. HRMS (ESI) m/z calcd for C17H25BClO3 ([M + H]+): 323.1580; found: 323.1552. [α]

25

D

–8.1 (c 1.20, CH2Cl2). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H

column: eluent, hexanes/iPrOH (99:1); flow rate = 0.2 mL/min; tR (1, anti- isomers mixture) =

50.4 min, tR (2, cis- isomer) = 57.4 min, tR (3, cis- isomer) = 61.5 min.

For (S,R)-2c, the diagnostic peaks on 1H NMR are: δ 2.21 (COCH3, s, 3H), 2.94 (BCH, d, J = 10.5

Hz, 1H).

S12

(3R,4R)-3-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-4-(m-tolyl)butan-2-one

[(R,R)-2d, syn]

S13


6H), 1.86 (COCH3, s, 3H), 2.26 (CH3, s, 3H), 2.46 (BCH, d, J = 10.6 Hz, 1H), 3.07 (CH, qd, J =

10.6 Hz, J = 6.9 Hz, 1H), 6.91 (Ar-H, d, J = 7.3 Hz, 1H), 6.98–7.11 (Ar-H, m, 3H). 13

C NMR (syn,

100 MHz, CDCl3) δ 16.7, 21.5, 24.6, 29.2, 49.9, 83.5, 125.9, 126.6, 128.3, 129.9, 137.9, 140.3,

213.0. HRMS (ESI) m/z calcd for C18H28BO3 ([M + H]+): 303.2126; found: 303.2123. [α]

25

D –18.4

(c 1.00, CH2Cl2). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H



For (S,R)-2d, the diagnostic peaks on 1H NMR are: δ 2.21 (COCH3, s, 3H), 2.96 (COCH, qd, J =

11.5 Hz, J = 7.4 Hz, 1H).

S14


-one [(R,R)-2e, syn]



1H), 7.05–7.19 (Ar-H, m, 4H). 13

C NMR (syn, 100 MHz, CDCl3) δ 16.6, 24.7, 29.1, 49.8, 83.7,

126.1, 127.4, 129.1, 129.7, 134.2, 142.8, 212.2. HRMS (ESI) m/z calcd for C17H25BClO3 ([M +

H]+): 323.1580; found: 323.1553. [α]

25




isomer) = 30.1 min.

For (S,R)-2e, the diagnostic peaks on 1H NMR are: δ 2.20 (COCH3, s, 3H), 2.94 (COCH, qd, J =

11.4 Hz, J = 7.3 Hz, 1H).

S15

(3R,4R)-4-(3-Bromophenyl)-3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-2

S16

-one [(R,R)-2f, syn]



1H), 7.05–7.13 (Ar-H, m, 2H), 7.22–7.25 (Ar-H, m, 1H), 7.35 (Ar-H, m, 1H). 13

C NMR (syn, 100

MHz, CDCl3) δ 16.6, 24.7, 29.1, 49.9, 83.8, 122.5, 127.8, 129.0, 130.0, 132.0, 143.1, 212.2.

HRMS (ESI) m/z calcd for C17H24BBrNaO3 ([M + Na]+): 389.0894; found: 389.0894. [α]

25

D –19.7

(c 1.00, CH2Cl2). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H



For (S,R)-2f, the diagnostic peaks on 1H NMR are: δ 2.20 (COCH3, s, 3H), 2.93 (COCH, qd, J =

11.0 Hz, J = 7.3 Hz, 1H).

S17

(3R,4R)-3-Methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-4-(p-tolyl)butan-2-one

[(R,R)-2g, syn]


6H), 1.85 (COCH3, s, 3H), 2.25 (CH3, s, 3H), 2.52 (BCH, d, J = 10.6 Hz, 1H), 3.05 (CH, qd, J =

10.6 Hz, J = 6.9 Hz, 1H), 7.00–7.07 (Ar-H, m, 4H). 13

C NMR (syn, 100 MHz, CDCl3) δ 16.7, 21.1,

24.6, 24.7, 29.1, 50.1, 83.5, 128.9, 129.2, 135.2, 137.3, 213.1. HRMS (ESI) m/z calcd for

C18H28BO3 ([M + H]+): 303.2126; found: 303.2121. [α]

25

D –19.9 (c 0.80, CH2Cl2). The

enantiomeric excess was determined by HPLC with a Chiralpak AS-H column: eluent,

hexanes/iPrOH (99:1); flow rate = 0.5 mL/min; tR (1, cis- isomer) = 26.1 min, tR (2, cis- isomer) =

29.6 min.

For (S,R)-2g, the diagnostic peaks on 1H NMR are: δ 2.20 (COCH3, s, 3H), 2.93 (COCH, qd, J =

11.0 Hz, J = 7.3 Hz, 1H).

S18

(3R,4R)-4-(4-Methoxyphenyl)-3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan

-2-one [(R,R)-2h, syn]

S19



1H), 3.73 (OCH3, s, 3H), 6.73–6.77 (Ar-H, m, 2H), 7.08–7.12 (Ar-H, m, 2H). 13

C NMR (syn, 100

MHz, CDCl3) δ 16.7, 24.6, 24.7, 29.2, 50.1, 55.2, 83.5, 113.9, 130.0, 132.4, 157.7, 213.1. HRMS

(ESI) m/z calcd for C18H28BO4 ([M + H]+): 319.2075; found: 319.2071. [α]

25

D –34.8 (c 1.50,

CH2Cl2). The enantiomeric excess was determined by HPLC with a Chiralpak OD-H column:

eluent, hexanes/iPrOH (99:1); flow rate = 0.5 mL/min; tR (1, anti- isomer) = 27.8 min, tR (2, anti-

isomer) = 29.5 min, tR (3, cis- isomer) = 30.7 min, tR (4, cis- isomer) = 35.1 min.

For (S,R)-2h, the diagnostic peaks on 1H NMR are: δ 2.19 (COCH3, s, 3H), 2.90 (COCH, qd, J =

11.0 Hz, J = 7.3 Hz, 1H).

S20

(3R,4R)-4-(4-Fluorophenyl)-3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-2

-one [(R,R)-2i, syn]



1H), 6.87–6.93 (Ar-H, m, 2H), 7.12–7.17 (Ar-H, m, 2H). 13


24.6, 24.7, 29.1, 50.1, 83.7, 115.2, 115.4, 130.4, 130.5, 136.2, 136.2, 160.1, 162.5, 212.6. HRMS

(ESI) m/z calcd for C17H25BFO3 ([M + H]+): 307.1875; found: 307.1873. [α]

25

D –38.9 (c 1.60,

CH2Cl2). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H column:

eluent, hexanes/iPrOH (99:1); flow rate = 0.5 mL/min; tR (1, anti- isomers mixture) = 19.4 min, tR

(2, cis- isomer) = 23.2 min, tR (3, cis- isomer) = 30.8 min.

For (S,R)-2i, the diagnostic peaks on 1H NMR are: δ 2.20 (COCH3, s, 3H), 2.91 (COCH, qd, J =

11.0 Hz, J = 7.4 Hz, 1H).

S21


-one [(R,R)-2j, syn]

S22



1H), 7.10–7.13 (Ar-H, m, 2H), 7.16–7.19 (Ar-H, m, 2H). 13



C17H25BClO3 ([M + H]+): 323.1580; found: 323.1580. [α]

25

D –10.5 (c 0.80, CH2Cl2). The


hexanes/iPrOH (99:1); flow rate = 0.5 mL/min; tR (1, anti- isomers mixture) = 20.6 min, tR (2, cis-

isomer) = 25.1 min, tR (3, cis- isomer) = 31.6 min.

For (S,R)-2j, the diagnostic peaks on 1H NMR are: δ 2.20 (COCH3, s, 3H), 2.92 (COCH, qd, J =

11.5 Hz, J = 7.3 Hz, 1H).

S23

(3R,4R)-4-(4-Bromophenyl)-3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-2

-one [(R,R)-2k, syn]



1H), 7.06 (Ar-H, d, J = 8.3 Hz, 2H), 7.32 (Ar-H, d, J = 8.3 Hz, 2H). 13

C NMR (syn, 100 MHz,

CDCl3) δ 16.7, 24.6, 24.7, 29.1, 49.8, 83.7, 119.7, 130.8, 131.5, 139.7, 212.3. HRMS (ESI) m/z

calcd for C17H25BBrO3 ([M + H]+): 367.1075; found: 367.1075. [α]

25

D –14.3 (c 0.60, CH2Cl2). The


hexanes/iPrOH (99:1); flow rate = 0.5 mL/min; tR (1, anti- isomers mixture) = 20.0 min, tR (2, cis-

isomer) = 24.9 min, tR (3, cis- isomer) = 30.4 min.

S24

(3S,4R)-4-(4-Bromophenyl)-3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-2

-one [(R,R)-2k, anti]

S25

White solid. 1H NMR (anti, 400 MHz, CDCl3) δ 0.97 (CH3, d, J = 7.4 Hz, 3H), 1.09 (CH3, s, 6H), 1.16 (CH3, s,


1H), 7.04 (Ar-H, d, J = 8.2 Hz, 2H), 7.35 (Ar-H, d, J = 8.3 Hz, 2H). 13


CDCl3) δ 16.2, 24.5, 24.6, 28.0, 50.7, 83.5, 119.5, 130.7, 131.6, 140.0, 212.8. [α]25

D –22.0 (c 0.30,

CH2Cl2). The enantiomeric excess was determined by HPLC with a Chiralpak AD column: eluent,

hexanes/iPrOH (99:1); flow rate = 0.5 mL/min; tR (1, anti- isomer) = 24.1 min, tR (2, anti- isomer)

= 28.9 min, tR (3, cis- isomers mixture) = 29.4 min.

S26

(3R,4R)-3-Methyl-4-(naphthalen-1-yl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-

2-one [(R,R)-2l, syn]

White solid, 99%, 83% ee, 14:1 dr. 1H NMR (syn, 400 MHz, CDCl3) δ 1.14 (CH3, s, 6H), 1.21 (CH3, s, 6H), 1.24 (CH3, d, J = 7.4 Hz,

3H), 1.87 (COCH3, s, 3H), 3.26 (CH, qd, J = 9.2 Hz, J = 7.4 Hz, 1H), 3.46 (BCH, d, J = 9.2 Hz,

1H), 7.34–7.50 (Ar-H, m, 4H), 7.64 (Ar-H, d, J = 8.2 Hz, 1H), 7.79 (Ar-H, dd, J = 9.6 Hz, J = 1.4

Hz, 1H), 8.18 (Ar-H, d, J = 8.2 Hz, 1H). 13

C NMR (syn, 100 MHz, CDCl3) δ 16.5, 24.6, 24.8, 28.6,

49.4, 83.6, 124.1, 125.4, 125.5, 125.9, 126.5, 126.6, 128.8, 132.2, 134.2, 137.1, 212.8. HRMS

(ESI) m/z calcd for C21H28BO3 ([M + H]+): 339.2126; found: 339.2122. [α]

25

D –30.6 (c 1.50,


eluent, hexanes/iPrOH (99:1); flow rate = 0.5 mL/min; tR (1, anti- isomer) = 26.0 min, tR (2, cis-

isomer and anti- isomer) = 30.5 min, tR (3, cis- isomer) = 36.2 min.

For (S,R)-2l, the diagnostic peak on 1H NMR is: δ 2.27 (COCH3, s, 3H).

S27

(3R,4R)-3-Methyl-4-(naphthalen-2-yl)-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-

2-one [(R,R)-2m, syn]

S28

White solid, 95%, 79% ee, 15:1 dr. 1H NMR (syn, 400 MHz, CDCl3) δ 1.16 (CH3, s, 6H), 1.21 (CH3, s, 6H), 1.21 (CH3, d, J = 6.9 Hz,


1H), 7.35–7.42 (Ar-H, m, 3H), 7.62 (Ar-H, s, 1H), 7.70–7.76 (Ar-H, m, 3H). 13

C NMR (syn, 100

MHz, CDCl3) δ 16.9, 24.7, 24.7, 29.1, 49.9, 83.7, 125.2, 125.8, 127.3, 127.6, 127.7, 127.7, 128.0,

132.0, 133.7, 138.2, 212.7. HRMS (ESI) m/z calcd for C21H28BO3 ([M + H]+): 339.2126; found:

339.2123. [α]25

D –16.3 (c 1.50, CH2Cl2). The enantiomeric excess was determined by HPLC with a

Chiralpak AS-H column: eluent, hexanes/iPrOH (99:1); flow rate = 0.5 mL/min; tR (1, anti-

isomers mixture) = 22.5 min, tR (2, cis- isomer) = 31.5 min, tR (3, cis- isomer) = 46.4 min.

For (S,R)-2l, the diagnostic peaks on 1H NMR are: δ 2.24 (COCH3, s, 3H), 2.45 (BCH, d, J = 11.5

Hz, 1H), 3.10 (CH, qd, J = 11.5 Hz, J = 7.4 Hz, 1H).

S29

(R)-3-((R)-phenyl(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)pentan-2-one [(R,R)-2n,

syn]

Colorless oil, 98%, 94% ee, 3.2:1 dr. 1H NMR (syn, 400 MHz, CDCl3) δ 0.87 (CH3, t, J = 7.3 Hz, 3H), 1.14 (CH3, s, 6H), 1.18 (CH3, s,

6H), 1.57–1.72 (CH2, m, 2H), 1.75 (COCH3, s, 3H), 2.55 (BCH, d, J = 11.4 Hz, 1H), 3.05 (CH,

ddd, J = 11.4 Hz, J = 9.6 Hz, J = 4.6 Hz, 1H), 7.07–7.11 (Ar-H, m, 1H), 7.17–7.22 (Ar-H, m, 4H). 13

C NMR (syn, 100 MHz, CDCl3) δ 16.9, 24.7, 24.7, 29.1, 49.9, 83.7, 125.2, 125.8, 127.3, 127.6,

127.7, 127.7, 128.0, 132.0, 133.7, 138.2, 212.7. HRMS (ESI) m/z calcd for C18H28BO3 ([M + H]+):

303.2126; found: 303.2123. [α]25




isomer) = 28.5 min.

S30

(S)-3-((R)-phenyl(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)pentan-2-one [(S,R)-2n,

syn]

S31

Colorless oil, 93% ee. 1H NMR (anti, 400 MHz, CDCl3) δ 0.70 (CH3, t, J = 7.4 Hz, 3H), 1.08 (CH3, s, 6H), 1.16 (CH3, s,

6H), 1.31–1.42 (CH2, m, 1H), 1.57–1.65 (CH2, m, 1H), 2.20 (COCH3, s, 3H), 2.49 (BCH, d, J =

11.4 Hz, 1H), 3.05 (CH, ddd, J = 11.4 Hz, J = 6.0 Hz, J = 4.1 Hz, 1H), 7.11–7.25 (Ar-H, m, 5H). 13

C NMR (syn, 100 MHz, CDCl3) δ 9.6, 22.1, 24.4, 24.6, 29.1, 56.3, 83.3, 125.6, 128.5, 129.0,

140.6, 213.0. HRMS (ESI) m/z calcd for C18H28BO3 ([M + H]+): 303.2126; found: 303.2123. [α]

25

D

–46.3 (c 0.60, CH2Cl2). The enantiomeric excess was determined by HPLC with a Chiralpak AD

column: eluent, hexanes/iPrOH (99:1); flow rate = 0.5 mL/min; tR (1, anti- isomer) = 20.5 min, tR

(2, anti- isomer) = 22.8 min, tR (3, cis- isomers mixture) = 25.8 min.

S32

(1R,2R)-2-Methyl-1-phenyl-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pentan-3-one

[(R,R)-2o, syn]

Colorless oil, 90%, 98% ee, 9:1 dr. 1H NMR (syn, 400 MHz, CDCl3) δ 0.76 (CH3, t, J = 7.3 Hz, 3H), 1.14 (CH3, d, J = 6.9 Hz, 3H),

1.16 (CH3, s, 6H), 1.21 (CH3, s, 6H), 1.92 (COCH2, qd, J = 17.9 Hz, J = 7.3 Hz, 1H), 2.24

(COCH2, qd, J = 17.9 Hz, J = 7.3 Hz, 1H), 2.59 (BCH, d, J = 10.6 Hz, 1H), 3.08 (CH, qd, J = 10.6

Hz, J = 7.3 Hz, 1H), 7.07–7.11 (Ar-H, m, 1H), 7.15–7.21 (Ar-H, m, 4H). 13


CDCl3) δ 7.4, 17.1, 24.6, 24.7, 35.7, 49.1, 83.6, 125.8, 128.4, 129.1, 140.6, 215.4. HRMS (ESI)

m/z calcd for C18H28BO3 ([M + H]+): 303.2126; found: 303.2122. [α]

25

D –30.5 (c 0.80, CH2Cl2).

The enantiomeric excess was determined by HPLC with a Chiralpak AD column: eluent,

hexanes/iPrOH (99:1); flow rate = 0.5 mL/min; tR (1, anti- isomer) = 21.3 min, tR (2, cis- isomer)

= 24.3 min, tR (3, cis- isomer and anti- isomer) = 28.1 min.

For (S,R)-2o, the diagnostic peaks on 1H NMR are: δ 2.32 (BCH, d, J = 11.4 Hz, 1H), 2.54

(COCH2, q, J = 7.3 Hz, 2H), 2.97 (COCH, qd, J = 11.4 Hz, J = 6.9 Hz, 1H).

S33

(2R,3R)-2-Methyl-1,3-diphenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propan-1-one

[(R,R)-2p, syn]

S34

Colorless oil, 89%, 90% ee, 14:1 dr. 1H NMR (syn, 400 MHz, CDCl3) δ 1.20 (CH3, s, 6H), 1.24 (CH3, s, 6H), 1.28 (CH3, t, J = 6.9 Hz,

3H), 2.88 (BCH, d, J = 9.6 Hz, 1H), 4.00 (CH, qd, J = 9.6 Hz, J = 6.9 Hz, 1H), 6.99–7.47 (Ar-H,

m, 8H), 7.80–7.82 (Ar-H, m, 2H). 13

C NMR (syn, 100 MHz, CDCl3) δ 18.1, 24.7, 24.8, 44.1, 83.5,

125.6, 128.3, 128.5, 129.2, 132.7, 136.9, 140.9, 204.3. HRMS (ESI) m/z calcd for C22H28BO3 ([M

+ H]+): 351.2126; found: 351.2125. [α]

25




isomer) = 28.5 min.

For (S,R)-2p, the diagnostic peaks on 1H NMR are: δ 2.53 (BCH, d, J = 11.0 Hz, 1H), 3.78

(COCH, qd, J = 11.0 Hz, J = 7.3 Hz, 1H).

S35

(2R,3S)-1-(4-Methoxyphenyl)-2-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan

-1-one [(R,R)-2q, syn]

Colorless oil, >99%, 93% ee, 3.1:1 dr. 1H NMR (syn, 400 MHz, CDCl3) δ 0.92 (CH3, d, J = 7.3 Hz, 3H), 1.18 (CH3, d, J = 6.9 Hz, 3H),

1.24 (CH3, s, 6H), 1.25 (CH3, s, 6H), 1.51 (BCH, qd, J = 8.7 Hz, J = 7.3 Hz, 1H), 3.47 (COCH, qd,

J = 8.7 Hz, J = 6.9 Hz, 1H), 3.84 (OCH3, s, 3H), 6.89–6.92 (Ar-H, m, 2H), 7.93–7.97 (Ar-H, m,

2H). 13

C NMR (syn, 100 MHz, CDCl3) δ 14.0, 17.6, 24.7, 24.9, 43.2, 55.5, 83.0, 113.7, 130.2,

130.7, 163.3, 203.8. HRMS (ESI) m/z calcd for C18H28BO4 ([M + H]+): 319.2075; found:

319.2073. [α]25

D –59.2 (c 0.50, CH2Cl2).The enantiomeric excess was determined by HPLC with a

Chiralpak AS-H column: eluent, hexanes/iPrOH (99:1); flow rate = 0.5 mL/min; tR (1, cis- isomer)

= 34.0 min, tR (2, cis- isomer) = 62.2 min.

For (S,R)-2q, the diagnostic peaks on 1H NMR are: δ 1.20 (CH3, d, J = 6.8 Hz, 3H), 3.84 (OCH3, s,

3H).

S36

(R)-2-((R)-Phenyl(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)cyclohexanone

[(R,R)-2r, syn]

S37

Colorless oil, >99%, 79% ee, 12:1 dr. 1H NMR (syn, 400 MHz, CDCl3) δ 1.19 (CH3, s, 6H), 1.23 (CH3, s, 6H), 1.48–1.71 (CH2, m, 3H),

1.78–2.02 (CH2, m, 3H), 2.21–2.39 (COCH2, m, 2H), 2.68 (BCH, d, J = 6.2 Hz, 1H), 2.72–2.78

(COCH, m, 1H), 7.09–7.23 (Ar-H, m, 5H). 13

C NMR (syn, 100 MHz, CDCl3) δ 24.7, 24.8, 25.2,


C19H28BO3 ([M + H]+): 315.2126; found: 315.2122. [α]

25

D –9.8 (c 0.60, CH2Cl2). The enantiomeric

excess was determined by HPLC with a Chiralpak AD column: eluent, hexanes/iPrOH (99:1);

flow rate = 0.5 mL/min; tR (1, cis- isomer) = 31.8 min, tR (2, cis- isomer) = 36.3 min.

For (S,R)-2r, the diagnostic peak on 1H NMR is: δ 2.17 (BCH, d, J = 11.4 Hz, 1H).

S38

(2R,3S)-Methyl

2-acetamido-3-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanoate [(R,S)-4a,

syn]

Colorless oil, >99%, 92% ee, 2.4:1 dr. 1H NMR (syn, 400 MHz, CDCl3) δ 1.23 (CH3, s, 6H), 1.25 (CH3, s, 6H), 1.95 (COCH3, s, 3H),

2.92 (BCH, d, J = 5.0 Hz, 1H), 3.63 (OCH3, s, 3H), 5.00 (NCH, dd, J = 8.7 Hz, J = 5.0 Hz, 1H),

6.35 (NH, d, J = 8.7 Hz, 1H), 7.15–7.26 (Ar-H, m, 5H). 13


24.6, 24.9, 52.2, 54.8, 84.2, 126.7, 128.6, 129.4, 137.6, 169.8, 172.6. HRMS (ESI) m/z calcd for

C18H27BNO5 ([M + H]+): 348.1977; found: 348.1977. [α]

25

D +22.3 (c 1.20, CH2Cl2). The


hexanes/iPrOH (90:10); flow rate = 1.0 mL/min; tR (1, anti- isomer) = 17.2 min, tR (2, anti- isomer)

= 24.8 min, tR (3, cis- isomer) = 29.0 min, tR (4, cis- isomer) = 55.4 min.

For (S,S)-4a, the diagnostic peaks on 1H NMR are: δ 1.16 (CH3, s, 6H), 1.18 (CH3, s, 6H), 1.82

(COCH3, s, 3H), 2.78 (BCH, d, J = 9.2 Hz, 1H), 3.68 (OCH3, s, 3H), 5.05 (NCH, dd, J = 9.2 Hz, J

= 7.8 Hz, 1H), 5.72 (NH, d, J = 7.8 Hz, 1H). The 13

C NMR: 23.1, 24.6, 24.7, 52.4, 54.0, 83.9,

126.5, 128.6, 129.3, 137.4, 172.7.

S39

(2R,3S)-Benzyl

S40

2-acetamido-3-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanoate [(R,S)-4b,

syn]

Colorless oil, >99%, 98% ee, 3:1 dr. 1H NMR (syn, 400 MHz, CDCl3) δ 1.16 (CH3, s, 6H), 1.19 (CH3, s, 6H), 1.95 (COCH3, s, 3H),

2.93 (BCH, d, J = 5.5 Hz, 1H), 5.00–5.09 (NCH, PhCH2, m, 3H), 6.39 (NH, d, J = 8.7 Hz, 1H),

7.13–7.22 (Ar-H, m, 7H), 7.26–7.33 (Ar-H, m, 3H). 13


24.6, 24.9, 54.9, 67.1, 84.2, 126.6, 128.3, 128.4, 128.6, 128.6, 129.4, 135.2, 137.6, 169.7, 172.1.

HRMS (ESI) m/z calcd for C24H31BNO5 ([M + H]+): 424.2290; found: 424.2286. [α]

25

D +15.2 (c

0.70, CH2Cl2). The enantiomeric excess was determined by HPLC with a Chiralpak OD-H column:

eluent, hexanes/iPrOH (90:10); flow rate = 0.5 mL/min; tR (1, cis- isomer) = 27.9 min, tR (2, cis-

isomer) = 30.7 min.

S41

(2S,3S)-Benzyl

2-acetamido-3-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanoate [(S,S)-4b,

anti]

Colorless oil. 1H NMR (syn, 400 MHz, CDCl3) δ 1.12 (CH3, s, 6H), 1.15 (CH3, s, 6H), 1.83 (COCH3, s, 3H),

2.84 (BCH, d, J = 8.7 Hz, 1H), 5.07–5.12 (NCH, PhCH2, m, 3H), 5.73 (NH, d, J = 8.2 Hz, 1H),

7.13–7.23 (Ar-H, m, 5H), 7.28–7.35 (Ar-H, m, 5H). 13


24.6, 24.7, 54.1, 67.2, 84.0, 126.6, 128.4, 128.4, 128.6, 129.5, 135.5, 137.4, 169.7, 172.0. HRMS

(ESI) m/z calcd for C24H31BNO5 ([M + H]+): 424.2290; found: 424.2286. [α]

25

D +18.3 (c 1.00,


eluent, hexanes/iPrOH (90:10); flow rate = 1.0 mL/min; tR (1, cis- isomer) = 17.2 min, tR (2, cis-

isomer) = 21.3 min.

S42

(2R,3S)-Isopropyl

2-acetamido-3-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanoate [(R,S)-4c,

S43

syn]

Colorless oil, >99%, 98% ee, 3.3:1 dr. 1H NMR (syn, 400 MHz, CDCl3) δ 1.05 (CH3, d, J = 6.4 Hz, 3H), 1.17 (CH3, d, J = 6.0 Hz, 3H),

1.22 (CH3, s, 6H), 1.24 (CH3, s, 6H), 1.96 (COCH3, s, 3H), 2.87 (BCH, d, J = 6.0 Hz, 1H),

4.85–4.94 (NCH, CHMe2, m, 2H), 6.35 (NH, d, J = 8.7 Hz, 1H), 7.14–7.25 (Ar-H, m, 5H). 13

C

NMR (syn, 100 MHz, CDCl3) δ 21.6, 21.8, 23.4, 24.7, 24.9, 54.9, 69.1, 84.2, 126.5, 128.5, 129.4,

137.8, 169.6, 171.8. HRMS (ESI) m/z calcd for C20H31BNO5 ([M + H]+): 376.2290; found:

376.2289. [α]25

D +14.8 (c 1.20, CH2Cl2). The enantiomeric excess was determined by HPLC with a

Chiralpak OD-H column: eluent, hexanes/iPrOH (90:10); flow rate = 0.5 mL/min; tR (1, cis-

isomer) = 19.6 min, tR (2, cis- isomer) = 22.1 min, tR (3, anti- isomer) = 27.8 min, tR (4, anti-

isomer) = 34.5 min.

For (S,S)-4c, the diagnostic peaks on 1H NMR are: δ 1.86 (COCH3, s, 3H), 2.83 (BCH, d, J = 8.2

Hz, 1H).

S44

(2R,3S)-Tert-butyl

2-acetamido-3-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanoate [(R,S)-4d,

syn]

Colorless oil, >99%, 97% ee, 16:1 dr. 1H NMR (syn, 400 MHz, CDCl3) δ 1.21 (CH3, s, 6H), 1.23 (CH3, s, 6H), 1.30 (C(CH3)3, s, 9H),

1.96 (COCH3, s, 3H), 2.83 (BCH, d, J = 6.4 Hz, 1H), 4.85 (NCH, dd, J = 6.4 Hz, J = 8.7 Hz, 1H),

6.35 (NH, d, J = 8.7 Hz, 1H), 7.15–7.23 (Ar-H, m, 5H). 13


24.7, 24.9, 27.9, 55.2, 81.8, 84.2, 126.4, 128.5, 129.4, 138.0, 169.6, 171.5. HRMS (ESI) m/z calcd

for C21H33BNO5 ([M + H]+): 390.2446; found: 390.2442. [α]

25

D +4.5 (c 1.20, CH2Cl2). The

enantiomeric excess was determined by HPLC with a Chiralpak OD-H column: eluent,

hexanes/iPrOH (90:10); flow rate = 0.5 mL/min; tR (1, cis- isomer) = 17.7 min, tR (2, cis- isomer)

= 22.7 min.

For (S,S)-4c, the diagnostic peaks on 1H NMR are: δ 1.85 (COCH3, s, 3H), 2.81 (BCH, d, J = 7.8

Hz, 1H), 4.89 (NCH, dd, J = 7.8 Hz, J = 8.7 Hz, 1H), 5.82 (NH, d, J = 8.7 Hz, 1H).

S45

(3R,4S)-3-Methoxy-4-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-2-one

[(R,S)-6, syn]

S46

Colorless oil, 89%, 94% ee, 4.9:1 dr. 1H NMR (syn, 400 MHz, CDCl3) δ 1.20 (CH3, s, 6H), 1.22 (CH3, s, 6H), 1.98 (COCH3, s, 3H),

2.70 (BCH, d, J = 9.6 Hz, 1H), 3.35 (OCH3, s, 1H), 3.96 (COCH, d, J = 9.6 Hz, 1H), 7.11–7.26

(Ar-H, m, 5H). 13

C NMR (syn, 100 MHz, CDCl3) δ 24.5, 24.8, 25.6, 58.4, 83.8, 89.8, 126.4, 128.6,

129.3, 136.9, 210.5. HRMS (ESI) m/z calcd for C17H26BO4 ([M + H]+): 305.1919; found:

305.1915. [α]25

D –9.5 (c 0.40, CH2Cl2). The enantiomeric excess was determined by HPLC with a

Chiralpak AS-H column: eluent, hexanes/iPrOH (99:1); flow rate = 0.5 mL/min; tR (1, anti- isomer)

= 29.7 min, tR (2, anti- isomer) = 32.1 min, tR (3, cis- isomer) = 35.5 min, tR (4, cis- isomer) = 38.5

min.

For (S,S)-6, the diagnostic peaks on 1H NMR are: δ 2.12 (COCH3, s, 3H), 3.18 (OCH3, s, 1H),

4.14 (COCH, d, J = 9.6 Hz, 1H).

S47

(3R,4S)-3-Chloro-4-phenyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-2-one

[(R,S)-8, syn]

Not able to separate, 15:1 dr. 1H NMR (syn, 400 MHz, CDCl3) δ 1.17 (CH3, s, 6H), 1.20 (CH3, s, 6H), 2.07 (COCH3, s, 3H),

3.02 (BCH, d, J = 11.2 Hz, 1H), 4.64 (COCH, d, J = 11.2 Hz, 1H), 7.07–7.23 (Ar-H, m, 5H).

For (S,S)-8, the diagnostic peak on 1H NMR is: δ 4.71 (COCH, d, J = 11.9 Hz, 1H).

C) Preparation of Optical Derivates

Procedure: The crude syn-8 mixture was then redissolved in anhydrous THF (2 mL). iPrOH (0.2

mL) and mCPBA (~77%, 155 mg, ~0.9 mmol) were then added and the reaction mixture was

stirred for 20 minutes. The mixture was concentrated under vacuum and redissolved in ethyl

S48

acetate. The organic layer was washed with saturated NaHCO3 for three times and the water layer

was extracted with ethyl acetate. The combined organic layer was washed with brine and dried

over Na2SO4. The crude product was concentrated and analyzed by 1H NMR, and then purified

through flash chromatography (ethyl acetate/hexanes = 1/6) with obvious isomerisation (from 15:1

dr to ~7:1 dr).

(3R,4S)-3-chloro-4-hydroxy-4-phenylbutan-2-one [(R,S)-9, syn]

Colorless oil, 83%, 78% ee, 15:1 dr. 1H NMR (syn, 400 MHz, CDCl3) δ 2.25 (COCH3, s, 3H), 2.83 (OH, d, J = 4.6 Hz, 1H), 4.43

(COCH, d, J = 4.6 Hz, 1H), 5.21 (OCH, t, J = 4.6 Hz, 1H), 7.30–7.38 (Ar-H, m, 5H). 13

C NMR

(syn, 100 MHz, CDCl3) δ 28.5, 68.5, 73.7, 126.5, 128.7, 128.7, 138.8, 203.2. [α]25

D +36.0 (c 0.30,

CH2Cl2). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H column:

eluent, hexanes/iPrOH (99:1); flow rate = 0.5 mL/min; tR (1, syn- isomer) = 45.8 min, tR (2, syn-

isomer) = 57.8 min.

For (S,S)-9, the diagnostic peaks on 1H NMR are: δ 2.33 (COCH3, s, 3H), 2.95 (OH, d, J = 4.1 Hz,

1H), 4.32 (COCH, d, J = 8.3 Hz, 1H), 5.01 (OCH, dd, J = 8.3 Hz, J = 4.1 Hz, 1H).

S49

Procedure: To a solution of syn-2a (80 mg, 0.28 mmol, 93% ee, 50:1 dr) in THF (2 mL) and H2O

(2 mL) was added NaBO3.4H2O (128 mg, 0.83 mmol). The reaction mixture was stirred for 30

minutes and then concentrated under vacuum. The residue was redissolved in ethyl acetate and

washed with saturated NaHCO3 for three times. The water layer was extracted with ethyl acetate.

The combined organic layer was washed with brine and dried over Na2SO4. The crude product

was concentrated and analyzed by 1H NMR and HPLC, and then purified through flash

chromatography (ethyl acetate/hexanes = 1/6).

(3R,4R)-4-hydroxy-3-methyl-4-phenylbutan-2-one [(R,R)-12, syn]

Colorless oil, 93%, 94% ee, pure diastereoisomer. 1H NMR (syn, 400 MHz, CDCl3) δ 1.07 (CH3, d, J = 7.3 Hz, 3H), 2.14 (COCH3, s, 3H), 2.82

(COCH, qd, J = 7.3 Hz, J = 3.7 Hz, 1H), 2.98 (OH, d, J = 3.0 Hz, 1H), 5.10 (OCH, dd, J = 3.7 Hz,

J = 3.0 Hz, 1H), 7.22–7.35 (Ar-H, m, 5H). [α]25

D +17.0 (c 0.20, CH2Cl2). The enantiomeric excess

S50

was determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/iPrOH (99:1); flow rate

= 0.5 mL/min; tR (1, syn- isomer) = 36.4 min, tR (2, anti- isomer) = 40.7 min, (3, syn- isomer) =

46.8 min, tR (4, anti- isomer) = 52.3 min.

For (S,R)-12, the diagnostic peaks on 1H NMR are: δ 0.92 (CH3, d, J = 7.4 Hz, 3H), 2.20 (COCH3,

s, 3H), 2.78 (OH, d, J = 4.2 Hz, 1H), 2.91 (COCH, qd, J = 8.7 Hz, J = 7.4 Hz, 1H), 5.10 (OCH, dd,

J = 8.7 Hz, J = 4.2 Hz, 1H).

Procedure: To a dry 10 mL Schlenk tube was added Bu4NBH4 (206 mg, 0.8 mmol). The tube was

then purged with argon and cooled down with an ice bath. Anhydrous acetic acid (1 mL) was

added and the mixture was stirred for one hour. Then the solution of syn-12 (18 mg, 0.1 mmol) in

acetic acid (0.3 mL) was added to the tube and the reaction mixture was stirred for 5 hours. The

reaction was quenched with 4 mL of 0.5 N aqueous sodium potassium tartrate and diluted with

water. The water phase was extracted with dichloromethane for three times. The combined organic

layer was washed with saturated Na2CO3 twice and then washed with brine. The extract was dried

over Na2SO4. The crude product was concentrated and analyzed by 1H NMR.

(1R,2S,3S)-2-Methyl-1-phenylbutane-1,3-diol (anti diol 13)

S51

Colorless oil, ~80%. 1H NMR (400 MHz, CDCl3) δ 0.79 (CH3, d, J = 6.9 Hz, 3H), 1.28 (CH3, d, J = 6.4 Hz, 3H),

1.78–1.85 (MeCH, m, 1H), 2.58 (OH, br, 1H), 3.15 (OH, br, 1H), 3.81 (OCH, qd, J = 6.4 Hz, J =

6.4 Hz, 1H), 5.10 (PhCH, d, J = 2.7 Hz, 1H), 7.20–7.34 (Ar-H, m, 5H). [α]25

D +25.5 (c 0.80,

CH2Cl2).

Procedure: To a dry 10 mL Schlenk tube was added syn-12 (18 mg, 0.1 mmol) in THF (0.5 mL)

under argon atmosphere. The mixture was cooled down with a dry ice/acetone bath. DIBAL

(diisobutylaluminium hydride, 1M in toluene, 0.3 mL) was added and the reaction mixture was

stirred overnight. Then the reaction was quenched with water and diluted with dichloromethane.

The organic phase was washed with 1 N HCl twice and the water phase was back extracted with

dichloromethane. The combined organic layer was washed with saturated NaHCO3 and brine. The

extract was dried over Na2SO4. The crude product was concentrated and analyzed by 1H NMR.

Colorless oil, ~95%. 1H NMR (400 MHz, CDCl3) δ 0.81 (CH3, d, J = 6.9 Hz, 3H), 1.21 (CH3, d, J = 6.4 Hz, 3H),

1.67–1.73 (MeCH, m, 1H), 2.56 (OH, br, 1H), 3.12 (OH, br, 1H), 4.22 (OCH, qd, J = 7.8 Hz, J =

6.4 Hz, 1H), 5.02 (PhCH, d, J = 2.3 Hz, 1H), 7.23–7.35 (Ar-H, m, 5H). [α]25

D +22.9 (c 0.80,

CH2Cl2).

D) Equilibrium experiment with (R,R)-2a

Procedure: To a dry 10 mL Schlenk tube was added syn-2a (20 mg, 0.069 mmol) in THF (0.5 mL).

under argon atmosphere. NaOtBu (0.03 M in THF, 1 mL) and MeOH (0.1 mL) were added via

syringe. The mixture was stirred for 3 hrs at room temperature and then cooled down with a dry

ice/glycol bath. The mixture was further stirred for 6 hrs at -20 ºC. Then the reaction was

S52

quenched by aqueous acetic acid (0.2 M, 2 mL). The mixture was diluted with water and extracted

with ethyl acetate for three times. The combined organic layer was washed with saturated

NaHCO3 and brine. The extract was dried over Na2SO4. The crude product was concentrated and

analyzed by 1H NMR. The mixture was then purified by flash chromatography and analyzed by

HPLC.

S53

HPLC Traces

(R,R)-2a

S54

(S,R)-2a

(S,R)-isomer + (S,S)-isomer

(R,S)-isomer

(R,R)-isomer

S55

(R,R)-2b

(S,R)-isomer + (R,S)-isomer

(R,R)-isomer

(S,S)-isomer

S56

(R,R)-2c

S57

(R,R)-2d

S58

(R,R)-2e

S59

(R,R)-2f

S60

(R,R)-2g

S61

(R,R)-2h

S62

(R,R)-2i

S63

(R,R)-2j

S64

(R,R)-2k

S65

(S,R)-2k

(S,R)-isomer

(R,S)-isomer syn-isomers

S66

(R,R)-2l

(S,S)-isomer

One anti isomer

(R,R)-isomer + one anti isomer

S67

(R,R)-2m

S68

(R,R)-2n

S69

(S,R)-2n

S70

(R,R)-2o

One anti isomer

(S,S)-isomer

(R,R)-isomer

+ one anti isomer

S71

(R,R)-2p

S72

(R,S)-2q

S73

(R,R)-2r

S74

(R,S)-4a

anti -isomers

syn -isomers

S75

(R,S)-4b

S76

(S,S)-4b

S77

(R,S)-4c

S78

(R,S)-4d

S79

(R,S)-6

Include an impurity

S80

(R,S)-9

S81

(R,R)-12

Include an impurity

S82

X-ray data for (S,R)-2k, anti

General Data Collection

Data was collected on a Bruker PLATFORM three circle diffractometer equipped with an

APEX II CCD detector and operated at 1500 W (50kV, 30 mA) to generate (graphite

monochromated) Mo Kα radiation (λ = 0.71073 Å). Crystals were transferred from the vial and

placed on a glass slide in Paratone® N oil. Two microscopes, a Motic SMZ-140 and an AmScope

XY-PRT polarizing microscope, were used to identify a suitable specimen for X-ray diffraction

from a representative sample of the material. The crystal and a small amount of the oil were

collected on a MῑTiGen cryoloop and transferred to the instrument where it was placed under a

cold nitrogen stream (Oxford) maintained at 100K throughout the duration of the experiment.

The sample was optically centered with the aid of a video camera to insure that no translations

were observed as the crystal was rotated through all positions.

A unit cell collection was then carried out. After it was determined that the unit cell was not

present in the CCDC database a sphere of data was collected. Omega scans were carried out

with a 30 sec/frame exposure time and a rotation of 0.33° per frame. After data collection, the

crystal was measured for size, morphology, and color. These values are reported in Table 1.

Refinement Details

After data collection, the unit cell was re-determined using a subset of the full data collection.

Initial unit cell determination led to an orthorhombic Bravais lattice, and ultimately the P212121

space group. However, multiple attempts to solve the structure were unsuccessful. The Bravais

lattice was then lowered to monoclinic with a β angle of 90.025°. Intensity data were corrected for

Lorentz, polarization, and background effects using the Bruker program APEX II. A

semi-empirical correction for adsorption was applied using the program SADABS. The

SHELXL-2014, series of programs was used for the solution and refinement of the crystal structure.

The structure was finally solved as a 2-component inversion twin in the space group P21 with the

twin law 1 0 0 0 1 0 0 0 -1 and a BASF of 0.38. Hydrogen atoms bonded to carbon atoms were

geometrically constrained using the appropriate AFIX commands.

S83

Crystal data and structure refinement for (S,R)-2k.

Identification code li14_06

Crystal Color colorless

Crystal Habit blade

Empirical formula C17 H24 B Br O3

Formula weight 367.08

Temperature 100(2) K

Wavelength 0.71073 A

Crystal system Monoclinic

Space group P21

Unit cell dimensions a = 10.203(2) Å alpha = 90°.

b = 12.287(3) Å beta = 90.025(3)°.

c = 14.177(3) Å gamma = 90°.

Volume 1777.3(7) Å3

Z 4

Calculated density 1.372 Mg/m3

Absorption coefficient 2.321 mm-1

F(000) 760

Crystal size 0.440 x 0.135 x 0.025 mm

Theta range for data collection 1.436 to 27.952°.

Limiting indices -13<=h<=13, -15<=k<=16, -18<=l<=18

Reflections collected / unique 21150 / 8402 [R(int) = 0.0249]

Completeness to theta = 25.242° 100.0 %

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 8402 / 1 / 398

Goodness-of-fit on F2 1.022

Final R indices [I>2sigma(I)] R1 = 0.0322, wR2 = 0.0789

R indices (all data) R1 = 0.0327, wR2 = 0.0792

Largest diff. peak and hole 0.377 and -0.212 e.A

-3

S84

Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å

2 x 10

3) for

li14_06. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

x y z U(eq)

Br(1) 5610(1) -151(1) 2263(1) 21(1)

O(1) 4759(4) 5670(3) 3479(3) 15(1)

O(2) 6912(4) 5316(3) 3839(3) 17(1)

O(3) 6046(5) 7126(4) 2053(3) 23(1)

C(1) 5766(6) 1399(5) 2231(4) 17(1)

C(2) 4659(5) 2056(6) 2283(4) 18(1)

C(3) 4802(5) 3171(5) 2246(5) 18(1)

C(4) 6045(5) 3652(5) 2161(4) 13(1)

C(5) 7133(5) 2973(5) 2124(4) 17(1)

C(6) 6998(6) 1840(5) 2158(5) 17(1)

C(7) 6223(4) 4890(5) 2133(4) 14(1)

C(8) 5386(6) 5435(4) 1367(4) 16(1)

C(9) 5920(6) 5180(6) 375(4) 24(1)

C(10) 5335(6) 6665(5) 1497(4) 16(1)

C(11) 4348(6) 7270(5) 911(5) 23(1)

C(12) 4852(5) 5710(5) 4508(4) 17(1)

C(13) 6364(6) 5860(5) 4669(4) 17(1)

C(14) 4347(6) 4619(5) 4857(4) 24(1)

C(15) 4006(6) 6636(5) 4875(4) 22(1)

C(16) 6856(6) 5312(6) 5558(4) 30(1)

C(17) 6809(6) 7033(5) 4629(5) 26(1)

B(1) 5967(6) 5340(5) 3154(5) 13(1)

Br(2) 388(1) 10151(1) 2628(1) 23(1)

O(4) -37(4) 4210(4) 1505(3) 16(1)

O(5) 2160(3) 4529(3) 1354(3) 15(1)

O(6) 1194(5) 2922(4) 3178(3) 30(1)

S85

C(18) 575(6) 8614(5) 2709(4) 18(1)

C(19) -519(6) 7953(5) 2696(4) 19(1)

C(20) -364(6) 6818(5) 2763(4) 18(1)

C(21) 889(5) 6365(5) 2846(4) 16(1)

C(22) 1967(5) 7063(5) 2838(4) 16(1)

C(23) 1824(5) 8179(5) 2764(5) 18(1)

C(24) 1110(5) 5137(5) 2927(4) 14(1)

C(25) 154(6) 4590(5) 3617(4) 15(1)

C(26) 298(6) 5020(5) 4626(4) 24(1)

C(27) 320(7) 3364(5) 3615(4) 20(1)

C(28) -655(8) 2724(6) 4198(5) 28(1)

C(29) 389(6) 3621(4) 656(4) 17(1)

C(30) 1709(5) 4186(5) 421(4) 16(1)

C(31) -670(6) 3727(6) -90(4) 28(1)

C(32) 565(7) 2431(4) 942(4) 24(1)

C(33) 1559(6) 5223(6) -159(4) 24(1)

C(34) 2740(6) 3449(5) -13(4) 23(1)

B(2) 1068(6) 4600(5) 1920(5) 14(1)

S86

Bond lengths [Å] and angles [°] for li14_06.

____________________________________________________________

Br(1)-C(1) 1.912(6)

O(1)-B(1) 1.376(8)

O(1)-C(12) 1.464(6)

O(2)-B(1) 1.369(7)

O(2)-C(13) 1.465(6)

O(3)-C(10) 1.211(7)

C(1)-C(6) 1.374(8)

C(1)-C(2) 1.391(8)

C(2)-C(3) 1.378(9)

C(3)-C(4) 1.405(8)

C(4)-C(5) 1.389(8)

C(4)-C(7) 1.532(8)

C(5)-C(6) 1.400(9)

C(7)-C(8) 1.535(7)

C(7)-B(1) 1.571(8)

C(8)-C(10) 1.524(8)

C(8)-C(9) 1.540(8)

C(10)-C(11) 1.502(8)

C(12)-C(14) 1.518(8)

C(12)-C(15) 1.520(8)

C(12)-C(13) 1.571(7)

C(13)-C(17) 1.512(9)

C(13)-C(16) 1.514(8)

Br(2)-C(18) 1.901(6)

O(4)-B(2) 1.359(7)

O(4)-C(29) 1.469(6)

O(5)-B(2) 1.377(7)

O(5)-C(30) 1.462(7)

O(6)-C(27) 1.214(8)

C(18)-C(19) 1.381(9)

C(18)-C(23) 1.384(8)

C(19)-C(20) 1.407(9)

C(20)-C(21) 1.399(8)

C(21)-C(22) 1.395(8)

C(21)-C(24) 1.529(8)

C(22)-C(23) 1.383(9)

C(24)-C(25) 1.537(8)

C(24)-B(2) 1.574(9)

C(25)-C(27) 1.516(8)

C(25)-C(26) 1.532(7)

C(27)-C(28) 1.514(9)

C(29)-C(31) 1.518(8)

S87

C(29)-C(32) 1.528(8)

C(29)-C(30) 1.551(8)

C(30)-C(34) 1.518(8)

C(30)-C(33) 1.525(8)

B(1)-O(1)-C(12) 106.7(4)

B(1)-O(2)-C(13) 106.9(4)

C(6)-C(1)-C(2) 121.2(6)

C(6)-C(1)-Br(1) 118.1(5)

C(2)-C(1)-Br(1) 120.7(5)

C(3)-C(2)-C(1) 119.3(5)

C(2)-C(3)-C(4) 121.2(5)

C(5)-C(4)-C(3) 118.2(5)

C(5)-C(4)-C(7) 120.0(5)

C(3)-C(4)-C(7) 121.8(5)

C(4)-C(5)-C(6) 121.1(5)

C(1)-C(6)-C(5) 119.0(5)

C(4)-C(7)-C(8) 112.7(4)

C(4)-C(7)-B(1) 107.8(5)

C(8)-C(7)-B(1) 113.9(5)

C(10)-C(8)-C(7) 111.4(5)

C(10)-C(8)-C(9) 109.0(5)

C(7)-C(8)-C(9) 111.1(5)

O(3)-C(10)-C(11) 122.0(6)

O(3)-C(10)-C(8) 121.5(5)

C(11)-C(10)-C(8) 116.5(5)

O(1)-C(12)-C(14) 105.9(5)

O(1)-C(12)-C(15) 109.2(4)

C(14)-C(12)-C(15) 110.9(5)

O(1)-C(12)-C(13) 102.2(4)

C(14)-C(12)-C(13) 112.9(5)

C(15)-C(12)-C(13) 114.9(5)

O(2)-C(13)-C(17) 106.8(5)

O(2)-C(13)-C(16) 109.8(5)

C(17)-C(13)-C(16) 110.9(5)

O(2)-C(13)-C(12) 101.8(4)

C(17)-C(13)-C(12) 113.7(5)

C(16)-C(13)-C(12) 113.2(5)

O(2)-B(1)-O(1) 113.5(5)

O(2)-B(1)-C(7) 121.9(5)

O(1)-B(1)-C(7) 124.1(5)

B(2)-O(4)-C(29) 106.4(4)

B(2)-O(5)-C(30) 106.9(4)

C(19)-C(18)-C(23) 121.2(6)

S88

C(19)-C(18)-Br(2) 120.1(5)

C(23)-C(18)-Br(2) 118.6(5)

C(18)-C(19)-C(20) 119.4(5)

C(21)-C(20)-C(19) 120.2(5)

C(22)-C(21)-C(20) 118.4(5)

C(22)-C(21)-C(24) 119.4(5)

C(20)-C(21)-C(24) 122.2(5)

C(23)-C(22)-C(21) 121.8(5)

C(22)-C(23)-C(18) 119.0(5)

C(21)-C(24)-C(25) 112.7(5)

C(21)-C(24)-B(2) 109.9(5)

C(25)-C(24)-B(2) 112.1(5)

C(27)-C(25)-C(26) 109.5(5)

C(27)-C(25)-C(24) 111.3(5)

C(26)-C(25)-C(24) 112.5(5)

O(6)-C(27)-C(28) 122.0(6)

O(6)-C(27)-C(25) 121.9(6)

C(28)-C(27)-C(25) 116.2(5)

O(4)-C(29)-C(31) 108.5(5)

O(4)-C(29)-C(32) 106.8(4)

C(31)-C(29)-C(32) 110.5(5)

O(4)-C(29)-C(30) 102.3(4)

C(31)-C(29)-C(30) 115.4(5)

C(32)-C(29)-C(30) 112.5(5)

O(5)-C(30)-C(34) 108.7(5)

O(5)-C(30)-C(33) 106.2(4)

C(34)-C(30)-C(33) 110.5(5)

O(5)-C(30)-C(29) 102.0(4)

C(34)-C(30)-C(29) 115.0(5)

C(33)-C(30)-C(29) 113.8(5)

O(4)-B(2)-O(5) 113.4(5)

O(4)-B(2)-C(24) 124.3(5)

O(5)-B(2)-C(24) 122.3(5)

_____________________________________________________________

Symmetry transformations used to generate equivalent atoms:

S89

Anisotropic displacement parameters (Å2 x 10

3) for li14_06. The anisotropic displacement factor

exponent takes the form: -2 π2 [ h

2 a*

2U

11 + ... + 2 h k a* b* U

12 ]

______________________________________________________________________

U11 U22 U33 U23 U13 U12

_______________________________________________________________________

Br(1) 32(1) 12(1) 18(1) 0(1) 2(1) -2(1)

O(1) 14(2) 15(2) 15(2) 0(2) -2(2) 2(2)

O(2) 14(2) 20(2) 17(2) -5(2) -2(1) 3(2)

O(3) 33(2) 16(2) 21(2) 0(2) -4(2) -7(2)

C(1) 26(3) 10(3) 15(3) 0(2) -1(2) 0(2)

C(2) 13(2) 22(3) 17(3) 4(2) 1(2) -5(2)

C(3) 12(2) 20(3) 22(3) 1(2) 0(2) 2(2)

C(4) 14(2) 15(3) 11(2) -1(2) 1(2) -1(2)

C(5) 12(2) 17(3) 21(3) -3(2) 2(2) -3(2)

C(6) 17(3) 15(3) 19(3) -3(2) 3(2) 3(2)

C(7) 11(2) 14(2) 17(2) -3(2) 1(2) -2(2)

C(8) 17(2) 15(3) 16(2) -1(2) 0(2) -3(2)

C(9) 36(3) 22(3) 15(2) -2(2) 1(2) 0(3)

C(10) 18(3) 13(3) 16(2) 2(2) 4(2) -5(2)

C(11) 23(3) 18(3) 26(3) 3(2) -3(3) -1(2)

C(12) 15(2) 22(3) 15(3) -1(2) -1(2) 4(2)

C(13) 14(2) 23(3) 14(2) -6(2) 0(2) 1(2)

C(14) 24(3) 26(3) 22(3) 7(2) 0(2) 1(3)

C(15) 17(3) 27(3) 22(3) -5(2) -1(2) 5(2)

C(16) 22(3) 45(4) 22(3) -1(3) -5(2) 9(3)

C(17) 22(3) 27(3) 30(3) -10(3) -2(3) -3(2)

B(1) 17(3) 6(3) 17(3) -1(2) -1(2) 0(2)

Br(2) 36(1) 11(1) 21(1) 0(1) -9(1) 4(1)

O(4) 15(2) 17(2) 15(2) -2(2) 1(2) -1(2)

O(5) 12(2) 17(2) 15(2) -2(1) -1(1) 1(1)

O(6) 43(3) 18(2) 27(2) 2(2) 7(2) 11(2)

C(18) 27(3) 12(3) 13(2) 0(2) -2(3) 2(2)

C(19) 18(3) 15(3) 25(3) 0(2) -1(3) 4(2)

C(20) 17(3) 14(3) 23(3) 1(2) 1(3) -2(2)

C(21) 19(3) 12(3) 15(2) -2(2) 0(2) -1(2)

C(22) 13(2) 18(3) 16(3) -2(2) -2(2) 2(2)

C(23) 17(3) 18(3) 18(3) 0(2) -3(2) -3(2)

C(24) 13(2) 13(3) 17(2) -2(2) -2(2) 0(2)

C(25) 16(2) 14(3) 16(2) 0(2) 1(2) 0(2)

C(26) 30(3) 26(3) 17(2) -6(2) 5(2) -4(3)

C(27) 29(3) 17(3) 14(2) 1(2) -3(2) 0(2)

C(28) 46(4) 16(3) 23(3) 3(2) 2(3) -7(3)

S90

C(29) 16(3) 20(3) 15(2) -2(2) 3(2) -1(2)

C(30) 17(3) 14(3) 16(3) 1(2) -1(2) -1(2)

C(31) 16(3) 44(4) 23(3) -6(3) -2(2) -3(3)

C(32) 33(3) 15(2) 25(3) -6(2) 9(3) -4(3)

C(33) 27(3) 24(3) 21(3) 7(3) 1(2) -1(3)

C(34) 23(3) 25(3) 21(3) -5(2) 6(2) 1(2)

B(2) 15(3) 9(3) 17(3) 3(2) 2(2) 0(2)

_______________________________________________________________________

Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å

2 x 10

3) for li14_06.

________________________________________________________________

x y z U(eq)

________________________________________________________________

H(2) 3813 1741 2343 21

H(3) 4046 3621 2278 22

H(5) 7983 3284 2074 20

H(6) 7748 1384 2130 21

H(7) 7162 5037 1978 17

H(8) 4473 5143 1412 19

H(9A) 5342 5501 -101 36

H(9B) 5957 4389 286 36

H(9C) 6802 5486 310 36

H(11A) 4349 8040 1090 34

H(11B) 3474 6962 1019 34

H(11C) 4575 7201 242 34

H(14A) 3452 4505 4626 36

H(14B) 4349 4612 5548 36

H(14C) 4915 4036 4621 36

H(15A) 4197 7300 4517 33

H(15B) 4196 6758 5544 33

H(15C) 3078 6447 4799 33

H(16A) 6725 4524 5508 44

H(16B) 6371 5591 6103 44

H(16C) 7792 5467 5638 44

H(17A) 7766 7059 4577 39

H(17B) 6533 7411 5204 39

H(17C) 6416 7389 4078 39

H(19) -1370 8262 2642 23

H(20) -1112 6358 2752 22

H(22) 2824 6764 2884 19

S91

H(23) 2572 8640 2752 22

H(24) 2014 5027 3182 17

H(25) -758 4755 3400 18

H(26A) -301 4624 5043 37

H(26B) 84 5797 4639 37

H(26C) 1202 4914 4840 37

H(28A) -658 1964 3990 42

H(28B) -1532 3035 4115 42

H(28C) -406 2760 4865 42

H(31A) -1495 3433 154 42

H(31B) -411 3320 -655 42

H(31C) -787 4496 -253 42

H(32A) 1299 2370 1386 37

H(32B) 748 1992 380 37

H(32C) -239 2168 1244 37

H(33A) 897 5693 133 36

H(33B) 1283 5036 -801 36

H(33C) 2400 5608 -182 36

H(34A) 3524 3877 -162 35

H(34B) 2393 3123 -592 35

H(34C) 2969 2873 436 35

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asymmetric catalytic enantio- and diastereoselective boron ...€¦ · jian-bo xie*, siqi lin, shuo...

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