a self-catalyzed reaction of 1,2-dibenzoyl o …chemical communications supporting information a...

Chemical Communications

Supporting Information

A Self-Catalyzed Reaction of 1,2-Dibenzoyl o-Carborane

with Hydrosilanes – Formation of New Hydrofuranes †

Kuldeep Jaiswal,a Solomon Volodarsky,a Vladimir Kampel,a and Roman

Dobrovetsky*a

Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2019

General experimental considerations

Commercial reagents were purchased from Sigma Aldrich, Strem or Apollo Scientific and used

without further purification unless indicated otherwise. NMR spectra were recorded at room

temperature using a Bruker AvanceIII-400 MHz spectrometer. Data for 1H NMR are reported as

follows: chemical shift (δ ppm), integration, multiplicity (s = singlet, d = doublet, t = triplet, q =

quartet, quin = quintet, m = multiplet, br = broad), coupling constant (Hz), assignment.

1

Ortho-carborane (2) (2.00 gr, 13.87 mmol, 1 eq.) dissolved in 100 mL of Et2O, was

treated with n-BuLi (11.30 mL, 30.51 mmol, 2.20 eq.) at 0 °C. After 30 min benzoyl

chloride (3.30 mL, 28.43 mmol, 2.05 eq.) in 20 mL was added to the stirring

solution at −78 °C. The solution was allowed to rich r.t. and left to stir for additional

30 min at r.t., and then was heated to reflux for additional 30 min. The organic phase

was washed with water and then brine, separated, dried over Na2SO4. The solvent was evaporated

and a mixture of oil and crystals was obtained. The crude was recrystallized from hexane to give

pure 1 (3.50 gr, 9.93 mmol) as a red solid in 73% yield. 1H NMR (400 MHz; CDCl3), δ1.75-3.57

(10H, br, B-H), 7.46 (4H, t, J = 7.7 Hz), 7.59 (2H, t, J = 7.4 Hz), 7.86 (4H, d, J = 7.7 Hz). 13C NMR

(100 MHz; CDCl3), δ 84.1, 128.3, 129.4, 133.1, 135.3, 185.5. 11B{1H} NMR (128 MHz; CDCl3),

δ 1.16, 7.98, 10.64. HRMS (ESI+): m/z calc’d for C16H20B10O2 : 376.2328 (M + Na+); found:

376.2330.

3

1,2-Dibenzoyl ortho-Carborane (1) (150 mg, 426 µmol, 1 eq.) and Et3SiH (98 mg,

852 µmol, 2 eq.) were dissolved in o-difluorobenzene, and heated at 140 °C for 96h.

o-difluorobenzene was evaporated and 3 was crystalized from hexane (170 mg, 363

µmol) in 85% yield.

1H NMR (400 MHz; C6D6), δ 0.42-0.59 (6H, overlapped quartet, J = 7.98 Hz), 0.87 (9H, t, J = 7.98

Hz), 1.96-3.77 (10H, br, B-H), 5.38 (1H, s), 7.07-7.19 (7H, m), 7.34-7.36 (3H, m). 13C NMR (100

MHz; CDCl3), δ 6.1, 6.9, 82.4, 84.4, 87.6, 106.5, 126.3, 129.5, 129.7, 135.6, 140.8. 11B{1H} NMR

(128 MHz; C6D6), δ 5.22, 6.19, 6.98, 8.96, 10.38, 12.39, 14.45. HRMS (ASAP+): m/z calc’d for

C2oH31B10O2Si: 440.3060 (M - Et+); found: 440.3064.

4

1,2-Dibenzoyl ortho-Carborane (1) (150 mg, 426 µmol, 1 eq.) and PhSiH3 (82.8

mg, 767 µmol, 1.8 eq.) were dissolved in o-difluorobenzene, and heated at 140 °C

for 48h. o-difluorobenzene was evaporated and 4 was crystalized from hexane (150

mg, 340 µmol) in 80% yield.

1H NMR (400 MHz; C6D6), δ 1.78-3.46 (13H, br, B-H), 5.21 (2H, s), 7.10-7.13 (8H, m), 7.33-

7.34 (4H, m). 13C NMR (100 MHz; CDCl3), δ 83.2, 126.0, 129.5, 130.7, 133.7, 135.0. 11B{1H}

NMR (128 MHz; C6D6), δ 5.50, 6.44, 7.58, 8.51, 9.55, 11.20, 12.76, 13.86. HRMS (ASAP+): m/z

calc’d for C16H21B10O: 337.2596 (M - H-); found: 337.2591

A solution of bromopentafluorobenzene (7.41 g, 30 mmol) in THF (100 mL) was

added dropwise to magnesium turnings (0.95 g, 39 mmol) in THF (50 mL) at 0 °C.

The mixture was stirred at room temperature for 1 h. Anhydrous copper(I) iodide

(11.43 g, 60 mmol) was added to the resulting dark brown solution, and the mixture

was stirred at room temperature for 1 h. After addition of dioxane (30 mL), the resulting suspension

was stirred at room temperature for 1 h. Phthaloyl dichloride (3.05 g, 30 mmol) was added to the

suspension at 0 °C, and stirred continue at room temperature overnight. The resulting suspension

was filtered through Celite, washed with CHCl3, and evaporated under reduced pressure. The

residue was dissolved in CHCl3, and the solution was passed through silica gel. After removal of

the solvent, the residue was purified by column chromatography on silica gel with n-

hexane/ethylacetate to give white crystalline product (1.05g, 15%). 1H NMR (400 MHz; CDCl3), δ

7.61-7.63 (4H, m), 7.73-7.75. (4H, m). 13C NMR (100 MHz; CDCl3), δ

113.4,130.3,133.2,136.4,138.8,138.9,142.0,143.6,144.6,146.1,186.1. 19F NMR (400 MHz, CDCl3)

δ 139.8 (4F, dd, J = 17.4, 8.7 Hz,), 148.3 (2F, t, J = 20.2 Hz), 160.3 (4F, dt, J = 20.2, 5.7 Hz),

HRMS (ASAP+): m/z calc’d for C20H4F10O2: 467.0130 (M + H+); found: 467.0128.

Figure.S1 Molecular structure of C6H4(CO(C6F5))2 (1941243).

Figure S2. 1H NMR of 1

Figure S3. 1H{11B} NMR of 1

Figure S4. 13C NMR of 1

Figure S5. 11B NMR of 1

Figure S6. 11B{1H} NMR of 1


Figure S8. 1H{11B} NMR of 3


Figure S16. 19F NMR; Reaction of 1 with [Bu4NH][B(C6F5)4]

Figure S17. 11B NMR; Reaction of 1 with Bu4NHB(C6F5)4

Figure S18. 19F NMR; Reaction of 1 with B(C6F5)3

Figure S19. 11B NMR; Reaction of 1 with B(C6F5)3

Figure S20. 1H NMR of C6H4(CO(C6F5))2

Figure S21. 13C NMR of C6H4(CO(C6F5))2

Figure S22. 19F NMR of C6H4(CO(C6F5))2

Figure S23. 1H NMR; Reaction of C6H4(CO(C6F5))2 with Et3SiH

Figure S24. 13C NMR; Reaction of C6H4(CO(C6F5))2 with Et3SiH

DFT calculations

DFT calculations were performed using Gaussian 09.2.1 Geometry optimization of all the

molecules, intermediates, and the transition state were carried out using the ωB97XD/def2-SVP

basis sets2 in 1,2-dichlorobenzene using the polarizable continuum model (PCM)3 implemented in

the Gaussian 09 software. Thermal energy corrections were extracted from the results of frequency

analysis performed at the same level of theory. Frequency analysis of all the molecules and

intermediates contained no imaginary frequency showing that these are energy minima. The

transition states geometries gave one imaginary frequency at expected reaction coordinates

confirming that it is a first-order saddle point.

1:

C 2.58508000 -1.71842000 -0.89348100

H 1.59752800 -1.89380100 -1.31709500

C 3.71630900 -2.25120400 -1.50824900

H 3.60749700 -2.82372200 -2.43141600

C 4.97933000 -2.05888200 -0.94851000

H 5.86301200 -2.47202700 -1.43918900

C 5.11161500 -1.34906500 0.24496300

H 6.09655500 -1.20328700 0.69270600

C 3.98324200 -0.82917100 0.87378200

H 4.08087400 -0.28010100 1.81271300

C 2.71759800 -0.99670300 0.29700800

C 1.56442000 -0.40818100 1.04908900

O 1.34313900 -0.70070200 2.19357100

C 0.80621000 0.79793300 0.42574300

B 1.67870700 2.00261100 -0.40574600

H 2.84664600 1.81726400 -0.57926300

B 1.05053100 2.27492500 1.23698700

H 1.79993700 2.27108400 2.16798000

B 0.51489900 2.68786700 -1.56273500

H 0.86538000 3.10391700 -2.63086900

B 0.83497400 3.51849200 -0.01492700

H 1.43809200 4.55417100 0.03958000

B -0.49939600 3.14037900 1.10862400

H -0.87255200 3.88502700 1.97069800

B -0.48883200 1.39601400 1.41182500

H -0.80263500 0.76349700 2.36966100

B -0.82975100 3.39615000 -0.62711400

H -1.45417100 4.33919400 -1.02705700

B -1.64190300 2.08582100 0.25365100

H -2.80136700 1.96603300 0.50668300

B -1.01711300 1.79920100 -1.38889000

H -1.73550900 1.47683700 -2.28688900

B 0.54288600 0.94784800 -1.26248900

H 0.83857400 0.05295000 -1.98526600

C -1.27919000 -0.75976600 -0.10551000

C -0.74416700 0.68066300 -0.13187800

O -0.46339500 -1.64926900 -0.02052600

C -2.73615800 -1.05156600 -0.10142800

C -3.70514900 -0.28160000 -0.75990700

H -3.42654300 0.60655100 -1.32288300

C -5.04135700 -0.67141000 -0.72863600

H -5.78821700 -0.07467600 -1.25498500

C -5.42304800 -1.81613600 -0.02949700

H -6.47449200 -2.10929300 0.00233200

C -4.46303300 -2.58927700 0.62570100

H -4.75882300 -3.48687100 1.17171000

C -3.12483000 -2.21746600 0.57922500

H -2.36398900 -2.81800600 1.08007900

Sum of electronic and zero-point Energies= -1019.470325

Sum of electronic and thermal Energies= -1019.449844

Sum of electronic and thermal Enthalpies= -1019.448900

Sum of electronic and thermal Free Energies= -1019.519030

:

H 0.00000400 0.00033500 1.87766000

Si 0.00004700 -0.00011900 0.37612000

C 1.78441500 -0.02330700 -0.22194300

H 2.33507200 0.86044500 0.13699500

H 2.31152900 -0.92133500 0.13662000

H 1.82368300 -0.02357500 -1.32321200

C -0.87204900 1.55685900 -0.22201300

H -0.88601300 1.59468300 -1.32322400

H -1.91434100 1.58852200 0.13219100

H -0.36111700 2.46201100 0.14220800

C -0.91251500 -1.53359200 -0.22194200

H -0.42422200 -2.45227600 0.13933700

H -1.95457800 -1.53817400 0.13430400

H -0.92977500 -1.56873200 -1.32317000





π-stacking:

C -1.39516800 2.94835200 1.37408000

H -0.64924900 2.45394700 1.99800700

C -1.62963500 4.31311700 1.50724900

H -1.07027500 4.88908200 2.24648000

C -2.56673200 4.94147700 0.68787600

H -2.74440000 6.01418100 0.78753900

C -3.26934500 4.20628300 -0.26724800

H -3.98441200 4.70301900 -0.92520600

C -3.06332100 2.83525500 -0.38513200

H -3.61045800 2.26708000 -1.13803000

C -2.12789700 2.20258400 0.44174200

C -1.83533900 0.75027900 0.35734100

O -0.70956400 0.31962500 0.28854900

C -2.98311900 -0.26001900 0.49739500

B -3.68340300 -0.47551500 2.04081300

H -3.32828000 0.26392400 2.91153800

B -4.63836800 0.14472400 0.68016400

H -4.95092100 1.29431500 0.65726200

B -4.03181200 -0.59719300 -0.81009900

H -3.85817600 -0.02697400 -1.83857700

B -5.50880400 -1.20976800 -0.06332900

H -6.55508300 -1.04565100 -0.62478800

B -5.30716300 -1.13266000 1.70992200

H -6.22300200 -0.89529200 2.44727600

B -5.11022700 -2.68110400 0.86096400

H -5.88186000 -3.59327600 0.96756800

B -4.29420400 -2.35796900 -0.69251300

H -4.35061000 -2.97999700 -1.71240100

B -3.37470200 -2.99611100 0.68730800

H -2.83802300 -4.05663000 0.59352500

B -3.98163900 -2.23025400 2.17129700

H -3.92309100 -2.78882300 3.23031900

B -2.49228500 -1.65145400 1.42912000

H -1.37207300 -1.66534400 1.82592800

C -2.78100700 -1.69952000 -0.26052900

C -1.63519800 -1.83818200 -1.29629900

O -1.56585200 -1.01688600 -2.17727900

C -0.75860000 -3.04159400 -1.28585900

C -0.26389100 -3.65725300 -0.12849800

H -0.48353700 -3.25146400 0.85625700

C 0.54604500 -4.78409700 -0.23023500

H 0.93805700 -5.24899700 0.67585000

C 0.85786100 -5.31375900 -1.48170500

H 1.48281700 -6.20604400 -1.55555200

C 0.38597900 -4.69464600 -2.63924800

H 0.63677700 -5.10047200 -3.62085300

C -0.40702400 -3.55652700 -2.54311300

H -0.78056900 -3.06455500 -3.44258600

C 1.45451700 0.16610500 2.82538500

H 0.84283100 0.49043200 1.98630900

C 0.84167200 -0.35894500 3.96058800

H -0.24627300 -0.44996000 3.99054700

C 1.60916600 -0.76258600 5.05358500

H 1.12466500 -1.18280800 5.93735000

C 2.99609300 -0.62051300 5.01801100

H 3.60271100 -0.92863700 5.87187100

C 3.61171800 -0.07726000 3.89288700

H 4.69617300 0.04645600 3.86543100

C 2.84693500 0.30356700 2.78210200

C 3.61112100 0.88591400 1.63040100

O 4.45160300 1.72856700 1.80627800

C 3.54370600 0.20735200 0.23136500

B 3.95905200 -1.43743900 0.12150300

H 4.17517400 -2.01550900 1.14671300

B 5.07163000 -0.17134800 -0.44301000

H 6.04034200 0.10194700 0.19959500

B 3.05942200 -2.04463400 -1.28544500

H 2.65581100 -3.16942700 -1.33398000

B 4.77733400 -1.59897300 -1.45169300

H 5.63513500 -2.42360000 -1.60965900

B 4.86090900 0.02014200 -2.19748000

H 5.76184800 0.38771000 -2.89854300

B 4.10644600 1.17003400 -1.08630400

H 4.31930900 2.32441400 -0.88557300

B 3.61648500 -1.14567700 -2.71927900

H 3.61550000 -1.63443300 -3.81548900

B 3.19370600 0.56401500 -2.49093400

H 2.84095700 1.36629100 -3.30326100

B 2.08620600 -0.70840600 -1.92971000

H 0.98500400 -0.83510200 -2.36027900

B 2.29317400 -0.90360000 -0.17801200

H 1.39102100 -1.07941000 0.56866700

C 1.56925000 1.81485400 -0.52796200

C 2.46654200 0.63688100 -0.94589700

O 1.70391500 2.22931800 0.60097500

C 0.69503400 2.51547100 -1.50229000

C 0.04207000 1.89411500 -2.57395400

H 0.15209800 0.82755500 -2.74909800

C -0.80250300 2.63464000 -3.39595500

H -1.32171700 2.13903600 -4.21826800

C -0.98510400 3.99831700 -3.17041500

H -1.64219600 4.57681300 -3.82319300

C -0.33613300 4.62332700 -2.10501300

H -0.48419700 5.68852300 -1.91960300

C 0.48981600 3.88380200 -1.26778300

H 0.98750400 4.35790800 -0.42092900





TS1:

O 1.49669100 -0.03755700 -1.28536400

C 5.78770300 -1.97206800 -2.87474800

H 6.65128400 -2.26820900 -3.47468400

C 5.62647900 -2.47011300 -1.58211700

H 6.36495900 -3.15653100 -1.16177000

C 4.52312500 -2.09209200 -0.81797700

H 4.43014700 -2.47989300 0.19415900

C 3.56086900 -1.21813500 -1.33102600

C 3.73891800 -0.71615600 -2.62256100

H 2.98599000 -0.02760100 -3.00618500

C 4.84078300 -1.08702700 -3.39004500

H 4.96164600 -0.68060500 -4.39696200

C 2.27768700 -0.77525900 -0.59844000

H 1.73332300 -1.85786700 -0.26889500

C 2.52460700 -0.19791700 0.86985800

C 2.67359100 1.43044200 0.92404100

C 2.79718500 2.23631200 -0.38784400

B 2.60018500 -0.31799500 3.64424400

H 2.57058000 -1.00293200 4.63106200

B 3.38850700 -0.91014900 2.16548600

H 3.87690600 -1.99001600 2.02729800

B 1.63509900 -0.73944000 2.21557000

H 0.96872400 -1.71210900 2.05935800

B 1.22978200 0.70880700 3.15901500

H 0.20308800 0.78604800 3.77741800

B 2.76639400 1.45045700 3.68247600

H 2.85970700 2.08285500 4.69949100

B 4.10551100 0.44374800 3.06562100

H 5.16259800 0.33096600 3.62302800

B 1.17375800 0.75470300 1.39326500

H 0.24555500 0.86553400 0.66681300

B 1.88715200 2.10467700 2.28682600

H 1.38265000 3.18170400 2.16715800

B 3.65576800 1.94270700 2.22216100

H 4.33682900 2.91227400 2.05201000

B 4.05640500 0.47629300 1.30009500

H 4.94184900 0.42786600 0.51005300

O 3.79493900 2.14548000 -1.05244700

C 1.75854500 3.27959900 -0.67279000

C 0.54931800 2.97179500 -1.29825600

C 2.07264100 4.60666400 -0.35780100

C -0.33820900 3.99908500 -1.61349100

H 0.33644300 1.93118600 -1.54273600

C 1.16837500 5.62361500 -0.65463300

H 3.02426000 4.84105900 0.12504100

C -0.03719800 5.31994000 -1.28690900

H -1.27700700 3.76575100 -2.11682000

H 1.41048000 6.65739800 -0.39961300

H -0.74606700 6.11506500 -1.52666800

O -2.24878900 0.33796800 1.39145500

C -2.39695100 5.29038200 1.22439300

H -2.29490400 6.36094500 1.41336600

C -3.32262900 4.83416800 0.28716300

H -3.95563500 5.54247100 -0.24990200

C -3.44089200 3.47330500 0.02218400

H -4.17396000 3.14393400 -0.70920100

C -2.64011600 2.55154700 0.71166200

C -1.72964800 3.02013900 1.67494500

H -1.11874500 2.30138900 2.22029600

C -1.59943700 4.38042900 1.91915700

H -0.87193900 4.73182700 2.65282900

C -2.67695200 1.07832700 0.53479900

C -3.16420600 0.41245700 -0.76175300

C -2.76615300 -1.20083000 -0.85679200

C -1.90950400 -1.86449000 0.24856200

B -4.35924200 0.32072900 -3.24877700

H -4.95253600 0.90427800 -4.11240900

B -3.10533500 1.14141100 -2.29995300

H -2.75584600 2.27739900 -2.36857700

B -4.65221100 0.70534300 -1.53755300

H -5.38775900 1.52161200 -1.07271500

B -5.16330700 -0.86781000 -2.18439100

H -6.32541500 -1.14783500 -2.26992700

B -3.91993800 -1.39452200 -3.35765500

H -4.18869900 -2.08844100 -4.29826900

B -2.64420600 -0.14998400 -3.41907100

H -1.98749100 0.08057400 -4.39449900

B -4.40827500 -0.77772700 -0.58505800

H -4.86461200 -0.92802700 0.50355400

B -3.94707700 -2.07433700 -1.72055600

H -4.14637100 -3.21435600 -1.43331200

B -2.40058600 -1.62866300 -2.46768900

H -1.56485700 -2.46284500 -2.64084600

B -1.88321700 -0.05862900 -1.82156900

H -0.76576500 0.17349500 -1.49047900

O -0.70801800 -1.89696800 0.04985700

Si 0.92232200 -3.56500600 -0.59298500

C 2.18582300 -4.27333100 0.58177200

H 3.21402000 -4.09930900 0.24591300

H 2.06198200 -3.84129500 1.58622800

H 2.00846100 -5.35785500 0.65820600

C -0.60965100 -4.61371400 -0.39511700

H -0.94549800 -4.69636200 0.64810000

H -1.44782300 -4.30115700 -1.03252300

H -0.29203700 -5.61849400 -0.72674800

C 1.25860900 -3.21820700 -2.38503900

H 0.99941900 -2.16852100 -2.60416400

H 2.32273300 -3.35737300 -2.62061600

H 0.64437300 -3.87960700 -3.01326900

C -2.50472700 -2.52725300 1.44119700

C -1.75925400 -2.45580500 2.62797500

C -3.69824400 -3.26048200 1.43051100

C -2.20029000 -3.09324200 3.78023100

H -0.84471800 -1.86646800 2.64474800

C -4.12656800 -3.91637100 2.58251200

H -4.29027700 -3.35815000 0.52471100

C -3.38469200 -3.83184700 3.75881200

H -1.61916000 -3.01065700 4.70040900

H -5.05055900 -4.49658700 2.55568700

H -3.73088200 -4.33912500 4.66156400





5:

O 4.41901500 -1.22904700 1.00181500

C 7.11202900 -2.63431900 -3.05724300

H 7.52224900 -3.14187600 -3.93335100

C 7.91207800 -1.76407600 -2.31580300

H 8.95095100 -1.59070200 -2.60533900

C 7.38600800 -1.12040000 -1.19646900

H 8.01633800 -0.44464700 -0.61097300

C 6.05817800 -1.33398700 -0.81652500

C 5.26018400 -2.21014700 -1.55544000

H 4.21985500 -2.34473300 -1.24531500

C 5.78834200 -2.85602200 -2.67321600

H 5.15980300 -3.53616600 -3.25308600

C 5.50394300 -0.60193800 0.39082900

H 6.31440700 -0.51642700 1.13459400

C 5.04004500 0.84352000 0.08288700

C 3.47894700 0.85897500 0.38575800

C 3.05419300 -0.66925900 0.70141500

B 5.07989100 3.53377300 -0.46987300

H 5.69573200 4.51353000 -0.79598200

B 5.47843300 1.93647300 -1.14903700

H 6.37228000 1.65351600 -1.89332400

B 5.81658300 2.28803500 0.55952300

H 6.93929600 2.22205700 0.97309600

B 4.49196000 3.30393500 1.19577000

H 4.67835200 4.09321600 2.08233100

B 3.32648900 3.55920500 -0.12675600

H 2.66135400 4.55947900 -0.20233100

B 3.93792000 2.73504100 -1.58155400

H 3.72705000 3.12469400 -2.69845100

B 4.52782800 1.58313700 1.54149400

H 4.73694300 1.00231100 2.55990400

B 2.99653500 2.32913200 1.11292400

H 2.11593000 2.31380400 1.92391700

B 2.65451300 1.97607000 -0.59115900

H 1.53547000 1.73680600 -0.94036400

B 3.97364800 1.01020100 -1.25587800

H 3.82910000 0.08512000 -1.98507000

O 2.45436400 -1.24656900 -0.27168400

C 2.28750500 -0.68927800 2.03547300

C 2.87542300 -0.94629600 3.27485000

C 0.91719400 -0.41327000 1.98802600

C 2.11141200 -0.91419600 4.44435400

H 3.94049800 -1.17558300 3.31475500

C 0.15506600 -0.36192600 3.15150100

H 0.45363700 -0.26088200 1.01106600

C 0.75165000 -0.61252900 4.38904000

H 2.58582900 -1.12293100 5.40633600

H -0.91093200 -0.13434100 3.09337100

H 0.15662700 -0.57889600 5.30472600

O -2.60931400 0.24775000 0.17160200

C -1.12994400 4.97296800 0.57310400

H -0.59274800 5.90800700 0.74337800

C -2.46013700 5.00932300 0.14716200

H -2.96173400 5.96419600 -0.01106600

C -3.14255000 3.82639300 -0.07843500

H -4.17812100 3.86470300 -0.40764900

C -2.49349700 2.58651000 0.13072800

C -1.14455600 2.56326300 0.56774700

H -0.61219900 1.62293600 0.71595400

C -0.47472600 3.75434600 0.78076200

H 0.56630600 3.73856500 1.10188700

C -3.17161500 1.35569200 -0.10224700

C -4.54044400 1.16686400 -0.68066000

C -4.68760200 -0.42561600 -0.76793000

C -3.36411600 -1.06191600 -0.27352200

B -7.03993800 1.54655800 -1.73517700

H -7.90081400 2.30186800 -2.08622900

B -5.32810800 1.96774200 -1.96915500

H -4.84281600 2.96794800 -2.40324000

B -6.02887200 1.93395900 -0.32513100

H -6.02168000 2.90900200 0.36302700

B -7.18977300 0.57795500 -0.24279300

H -8.13670800 0.62759900 0.48778300

B -7.19276100 -0.23057200 -1.83681100

H -8.17175800 -0.77176000 -2.26563200

B -6.05286300 0.63180300 -2.90849900

H -6.18819400 0.71938400 -4.09477300

B -5.59517300 0.38994900 0.45723100

H -5.20700600 0.31483100 1.57844100

B -6.27792500 -0.94632300 -0.48894100

H -6.44021100 -1.98970500 0.06839600

B -5.57317600 -0.91317300 -2.12906300

H -5.27062600 -1.93499300 -2.66589400

B -4.43805200 0.45074300 -2.25741500

H -3.35788800 0.40379300 -2.75234400

O -2.70456100 -1.59380400 -1.27727500

Si -1.01587600 -2.06079000 -1.48793800

C -0.38278300 -2.86879300 0.06335100

H -0.77794800 -2.40392400 0.97750700

H -0.62678700 -3.94130900 0.08975000

H 0.71081300 -2.71425400 0.07206600

C -1.13394100 -3.23889300 -2.92370300

H -1.73020000 -4.12539500 -2.65899600

H -1.58992500 -2.75483600 -3.80035500

H -0.12419300 -3.57760400 -3.20503400

C -0.13832600 -0.47650300 -1.91280200

H -0.48493900 0.35220200 -1.27845000

H 0.93526900 -0.61295400 -1.69490600

H -0.29392700 -0.19053600 -2.96377000

C -3.46687400 -1.93262600 0.95901900

C -3.30879400 -1.44637800 2.25692400

C -3.72448400 -3.29029800 0.74772000

C -3.39131400 -2.31835100 3.34041500

H -3.10280300 -0.39049800 2.43160800

C -3.81926000 -4.15563900 1.83349100

H -3.83770900 -3.67276300 -0.26838900

C -3.64699700 -3.67203900 3.13065100

H -3.24784500 -1.93450900 4.35191800

H -4.01744900 -5.21529700 1.66392700

H -3.70792100 -4.35479900 3.98026700





TS2:

O 4.17150800 -1.41857800 0.78583200

C 5.19769100 -3.25520200 -3.80807600

H 5.21749700 -3.82218100 -4.73571600

C 6.30952100 -2.49497900 -3.42977000

H 7.19544100 -2.47015300 -4.06156800

C 6.28535900 -1.77217100 -2.23461100

H 7.15260700 -1.17478500 -1.93980500

C 5.14883600 -1.79600900 -1.41615600

C 4.03912600 -2.55292100 -1.79213300

H 3.16369000 -2.54432200 -1.14398100

C 4.06625800 -3.28761600 -2.98617600

H 3.20144000 -3.87889300 -3.27613800

C 5.13437300 -0.99034500 -0.13650800

H 6.11619000 -1.08427400 0.34933700

C 4.88292300 0.52797200 -0.33014100

C 3.49828500 0.82032100 0.39328200

C 2.92053300 -0.62100700 0.85969700

B 5.26590900 3.17124100 -0.95177700

H 5.93224300 4.02605900 -1.46738400

B 5.15349900 1.54299100 -1.66935700

H 5.73951000 1.11875200 -2.62209100

B 6.01474600 1.79179100 -0.12974500

H 7.17350500 1.50986900 -0.03649600

B 5.12591700 3.01999400 0.81057700

H 5.68901900 3.74082200 1.59611600

B 3.70824500 3.51274300 -0.14125200

H 3.23053000 4.61698300 -0.06405500

B 3.73142700 2.62670000 -1.68426500

H 3.29134100 3.06891900 -2.70996600

B 4.93302700 1.31394100 1.19620900

H 5.29615300 0.67322000 2.12885800

B 3.51360900 2.34015400 1.17219000

H 2.89980400 2.48635300 2.19743600

B 2.65373000 2.09235600 -0.36046200

H 1.45893900 2.07215700 -0.37086900

B 3.54540500 0.91824700 -1.32963800

H 3.04839400 0.03940900 -1.95684300

O 1.96075700 -1.06062400 0.11956800

C 2.57163800 -0.53348500 2.36282200

C 3.32879700 -1.12086000 3.37114400

C 1.42018000 0.18946600 2.69849300

C 2.92532300 -1.00680900 4.71009900

H 4.22879000 -1.68055700 3.10708600

C 1.02855300 0.32001900 4.02860900

H 0.85591200 0.63825000 1.89048600

C 1.78062300 -0.28403600 5.04499000

H 3.52052100 -1.46921700 5.49795700

H 0.12605800 0.89187000 4.27459300

H 1.47690600 -0.18160200 6.08649100

O -2.70835900 0.32392700 0.59863600

C -0.57268300 4.73724800 0.84292700

H 0.11996500 5.56663900 0.99877900

C -1.71929100 4.92829000 0.07680300

H -1.94503900 5.90974200 -0.34899000

C -2.58459400 3.86438000 -0.15943500

H -3.47700400 4.01751100 -0.76854600

C -2.28757800 2.60061200 0.38444500

C -1.13481800 2.43089400 1.18995700

H -0.91978400 1.44483500 1.60699200

C -0.27376800 3.49704700 1.41090800

H 0.63993600 3.34426500 1.99226000

C -3.04433600 1.41357000 0.07692200

C -4.21184900 1.27686200 -0.85301200

C -4.46227400 -0.31535900 -0.94222100

C -3.36150700 -1.06793300 -0.15362300

B -6.36737600 1.80570900 -2.47181500

H -7.05483700 2.61341300 -3.02455100

B -4.61320000 2.08187700 -2.31248400

H -3.96518900 3.02244000 -2.64875800

B -5.67485400 2.16213900 -0.87404400

H -5.73088900 3.16076400 -0.21753200

B -6.92741200 0.90615800 -1.03661900

H -8.01435800 1.05411300 -0.54236700

B -6.64042400 0.03858500 -2.57476800

H -7.53532800 -0.43510900 -3.20658800

B -5.21508500 0.77439100 -3.36918800

H -5.06372600 0.82676100 -4.55488000

B -5.56074200 0.62239400 0.01015000

H -5.45030100 0.55870400 1.19326700

B -6.11378500 -0.69733300 -1.04097500

H -6.49448600 -1.69550000 -0.51460800

B -5.05251500 -0.77565600 -2.46167700

H -4.71764700 -1.83054900 -2.90889500

B -3.81728000 0.49970300 -2.34590900

H -2.66642100 0.34376600 -2.59122200

O -2.40621000 -1.54201700 -0.87967700

Si -0.56588100 -1.63617300 -0.51758700

C -0.59270900 -2.00367200 1.30818100

H -0.97440000 -1.18042400 1.93572900

H -1.22436000 -2.89601800 1.49333500

H 0.44043900 -2.20440000 1.59637900

C -0.07644300 -3.11311400 -1.52214900

H -0.55960000 -4.03615100 -1.16481600

H -0.30369100 -2.97977900 -2.58661600

H 1.01431900 -3.23633700 -1.41267100

C -0.15969600 -0.04224500 -1.40904400

H -0.35615300 0.85829900 -0.79557800

H 0.93874900 -0.06619400 -1.63820900

H -0.75383000 0.01167000 -2.36468900

C -3.84132900 -1.93510500 0.98555400

C -4.03930400 -1.48756800 2.29590400

C -4.09227300 -3.26800500 0.66304200

C -4.49046400 -2.37076800 3.26830000

H -3.80756200 -0.45896800 2.56358700

C -4.55339200 -4.14406900 1.63556200

H -3.91684100 -3.61761300 -0.35927200

C -4.75234100 -3.69633800 2.93502200

H -4.62536700 -2.02030600 4.29545500

H -4.75289000 -5.19415700 1.37953300

H -5.11585400 -4.39635000 3.70797500





3c:

O -0.07198200 -0.53143000 -1.05930300

C -4.63380900 -2.61384000 -0.59122100

H -5.47522900 -3.29000900 -0.42585300

C -4.80453900 -1.45750600 -1.35394700

H -5.77904300 -1.22682100 -1.78905500

C -3.72846700 -0.59939400 -1.57194600

H -3.86425200 0.30167200 -2.17623100

C -2.47750700 -0.88586700 -1.01825700

C -2.30947600 -2.04415800 -0.26035200

H -1.32921400 -2.26078400 0.16240800

C -3.38360700 -2.90656000 -0.04701600

H -3.24110500 -3.81269500 0.54561100

C -1.33474600 0.07778100 -1.24084600

H -1.38841600 0.45242100 -2.27500400

C -1.34074800 1.29994100 -0.30852600

C 0.08167800 1.29331700 0.41483000

C 0.80206700 0.00006800 -0.07761700

B -2.07951600 3.62750500 0.93093400

H -2.90066400 4.48513100 1.10818300

B -2.57163300 1.93668400 0.67913200

H -3.67358000 1.48261400 0.58521600

B -1.87663000 2.87401400 -0.66680300

H -2.50922200 3.04275200 -1.66863900

B -0.59318000 3.93134600 -0.00540800

H -0.33166000 4.98575900 -0.51411200

B -0.49025500 3.62189500 1.74812700

H -0.15086600 4.47440600 2.52230100

B -1.71649900 2.40373800 2.17896400

H -2.26309500 2.36395500 3.24611800

B -0.16674300 2.44631500 -0.83391700

H 0.35606700 2.23475400 -1.88407100

B 0.68988500 2.87437600 0.65026900

H 1.86753100 3.06166300 0.58840200

B 0.00033500 1.92465100 1.99107300

H 0.71897200 1.47209300 2.83223900

B -1.30886100 0.90610700 1.36696800

H -1.48169200 -0.22837800 1.67290400

O 0.91799400 -0.85415500 0.98777200

Si 1.59584100 -2.42558200 1.08958500

C 1.56706900 -3.25297600 -0.58686400

H 0.54879200 -3.31756000 -0.99654300

H 2.19148100 -2.70219500 -1.30675900

H 1.97253200 -4.27338400 -0.49405400

C 3.34313100 -2.29994100 1.74317800

H 4.02916400 -1.87561400 0.99547700

H 3.38161800 -1.67215200 2.64705000

H 3.70703700 -3.30508800 2.01111600

C 0.50286300 -3.29227200 2.33286500

H -0.53161400 -3.39719100 1.97281500

H 0.89420900 -4.30052200 2.54145800

H 0.47903000 -2.73297300 3.28101000

C 2.16018100 0.28394700 -0.71287800

C 2.36245400 0.16295200 -2.08733200

C 3.22415400 0.66145000 0.11162900

C 3.62232500 0.40975200 -2.63340400

H 1.53077300 -0.13573500 -2.72589400

C 4.47921600 0.91568400 -0.43462600

H 3.06948300 0.74983000 1.18891900

C 4.68151900 0.78732000 -1.80973000

H 3.77531600 0.30357500 -3.70928700

H 5.30384900 1.21147100 0.21704500

H 5.66686700 0.98047900 -2.23906400





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a self-catalyzed reaction of 1,2-dibenzoyl o …chemical communications supporting information a...

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