Supporting Information for

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1 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. Contents General Information Supplementary Schemes and Table Preparation of L3 S2 S3 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 X-ray data for (S,R)-2k, anti S53-S81 S82-S91 S1

2 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, n PrOH, i PrOH, t BuOH, CF 3 CH 2 OH and (CF 3 ) 2 CHOH were dried over 4 Å molecular sieve. B 2 Pin 2 was purchased from Frontier Scientific. CuCl (anhydrous, beads, 99.99% trace metals basis), silver bis(trifluoromethanesulfonyl)imide (AgNTf 2 ), (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 literature1 1. 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 1 H, 13 C and 31 P 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 = Å). All the glasswares used were dried overnight at 110 o C. The NMR spectra were recorded at 400, 100, and 162 MHz for 1 H, 13 C, and 31 P, 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). S2

3 Supplementary Schemes and Table Scheme S1. Screening the Chiral Ligands Scheme S2. Synthesis of 1,3-Diols Table S1. Influence of Bulk and pk a of the Additives 2n 4b entry additive (pk a ) conv dr (%) (syn/anti) ee (%, syn/anti) 1 MeOH (15.54) 40 5:1 87/87 2 t BuOH (17.0) 71 12:1 80/- 3 TFE (12.5) :1 94/93 4 HFIP (9.3) 99 1:1.4 93/83 5 MeOH >99 1.9:1 89/89 6 i PrOH (16.5) >99 2.1:1 85/90 7 BnOH (15.0) >99 1.2:1 91/91 8 t BuOH >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 C 6 F 5 OH (4.46) >99 1:1.4 89/88 S3

4 Preparation of L3 (S)-(R)-L2 (200 mg, 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, 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, mmol) and AcOH (42 mg, mmol) were added then. The reaction mixture was stired overnight before it was diluted by dichloromethane (DCM). The organic layer was washed by saturated Na 2 CO 3 and brine successively and dried by Na 2 SO 4. 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). 1 H NMR (major, 400 MHz, CDCl 3 ) δ 1.44 (CH 3, d, J = 6.9 Hz, 3H), 3.94 (NCH 3, s, 3H), 3.98 (NCH, m, 1H), 4.49 (PhCH 2, m, 2H), (Ar-H, m, 18H). 31 P NMR (162 MHz, CDCl 3 ) δ (major), (minor). HRMS (ESI) m/z calcd for C 32 H 33 FeNP ([M + H] + ): ; found: [α] 25 D (c 1.80, CH 2 Cl 2 ). S4

5 Synthesis and Characterization of Products A) Preparation of Racemic Products For (rac)-2a-r: CuCl (6 mg, 0.06 mmol), NaO t Bu (5.8 mg, 0.06 mmol), bis(pinacolato)diboron (B 2 pin 2, 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 1 H 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 t Bu was used intead of CuCl/NaO t Bu and THF was excluded. The anti-4 and 6 are unstable in the presence of NaO t Bu. For (rac)-8 and (rac)-9: CuCl (3.0 mg, 0.03 mmol) and (rac)-l1 (15.7 mg, 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 AgNTf 2 (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 B 2 pin 2 (152 mg, 0.6 mmol) in toluene (1 ml) was added, followed by the addition of CF 3 CH 2 OH (0.10 ml). The reaction mixture was stirred vigorously for 48 hours. After filtration S5

6 through celite and wash with hexanes, the filtrate was concentrated and the residue was analyzed with a 1 H 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). i PrOH (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 NaHCO 3 for three times and the water layer was extracted with ethyl acetate. The combined organic layer was washed with brine and dried over Na 2 SO 4. The crude product was concentrated and purified through flash chromatography. B) Preparation of Optical Products General produre (5 mol% catalyst): CuCl (7.6 mg, mmol) and (S)-(R)-L1 (67.8 mg, 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 (~ M) was obtained then. Into a another dry 10 ml Schlenk tube was added AgNTf 2 (3.8 mg, 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 B 2 pin 2 (194 mg, 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 1 H 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). S6

7 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. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.16 (CH 3, d, J = 6.9 Hz, 3H), 1.16 (CH 3, s, 6H), 1.20 (CH 3, s, 6H), 1.85 (COCH 3, s, 3H), 2.57 (BCH, d, J = 10.5 Hz, 1H), 3.09 (CH, qd, J = 10.5 Hz, J = 6.9 Hz, 1H), (Ar-H, m, 1H), (Ar-H, m, 4H). 13 C NMR (syn, 100 MHz, CDCl 3 ) δ 16.7, 24.6, 24.7, 29.1, 29.8, 50.0, 83.6, 125.8, 128.5, 129.0, 140.5, HRMS (ESI) m/z calcd for C 17 H 25 BNaO 3 ([M + Na] + ): ; found: [α] 25 D 38.8 (c 1.20, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AD column: eluent, hexanes/ i PrOH (98:2); flow rate = 0.5 ml/min; t R (1, anti- isomer) = 22.0 min, t R (2, cis- isomer) = 25.2 min, t R (3, anti- isomer) = 25.8 min, t R (4, cis- isomer) = 26.6 min. S7

8 (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. 1 H NMR (anti, 400 MHz, CDCl 3 ) δ 0.97 (CH 3, d, J = 6.8 Hz, 3H), 1.09 (CH 3, s, 6H), 1.17 (CH 3, s, 6H), 2.21 (COCH 3, s, 3H), 2.27 (BCH, d, J = 11.4 Hz, 1H), 2.97 (CH, qd, J = 11.4 Hz, J = 6.8 Hz, 1H), (Ar-H, m, 5H). 13 C NMR (anti, 100 MHz, CDCl 3 ) δ 16.3, 24.5, 24.6, 28.1, 29.8, 50.7, 83.3, 125.7, 128.5, 129.0, 140.7, [α] 25 D 20.8 (c 0.60, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AD column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, anti- isomer) = 23.5 min, t R (2, cis- isomer + anti- isomer) = 28.3 min, t R (3, cis- isomer) = 29.8 min. S8

9 (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] S9

10 Colorless oil, >99%, 93% ee, 33:1 dr. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.18 (CH 3, d, J = 7.4 Hz, 3H), 1.18 (CH 3, s, 6H), 1.22 (CH 3, s, 6H), 1.96 (COCH 3, s, 3H), 2.88(BCH, d, J = 8.7 Hz, 1H), 3.07 (CH, qd, J = 8.7 Hz, J = 7.4 Hz, 1H), (Ar-H, m, 2H), (Ar-H, m, 1H), (Ar-H, m, 1H). 13 C NMR (syn, 100 MHz, CDCl 3 ) 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, HRMS (ESI) m/z calcd for C 17 H 24 BFNaO 3 ([M + Na] + ): ; found: [α] 25 D 27.0 (c 1.10, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, anti- isomers mixture) = 19.3 min, t R (2, cis- isomer) = 22.7 min, t R (3, cis- isomer) = 24.4 min. For (S,R)-2b, the diagnostic peaks on 1 H NMR are: δ 2.17 (COCH 3, s, 3H), 2.63 (BCH, d, J = 11.0 Hz, 1H). S10

11 (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] Colorless oil, >99%, 97% ee, 70:1 dr. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.18 (CH 3, d, J = 6.9 Hz, 3H), 1.18 (CH 3, s, 6H), 1.22 (CH 3, s, 6H), 1.99 (COCH 3, s, 3H), 3.11 (CH, qd, J = 8.2 Hz, J = 6.9 Hz, 1H), 3.14(BCH, d, J = 8.2 Hz, 1H), (Ar-H, m, 1H), (Ar-H, m, 1H), (Ar-H, m, 2H). 13 C NMR (syn, 100 MHz, CDCl 3 ) 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, HRMS (ESI) m/z calcd for C 17 H 25 BClO 3 ([M + H] + ): ; found: [α] 25 D 8.1 (c 1.20, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.2 ml/min; t R (1, anti- isomers mixture) = 50.4 min, t R (2, cis- isomer) = 57.4 min, t R (3, cis- isomer) = 61.5 min. For (S,R)-2c, the diagnostic peaks on 1 H NMR are: δ 2.21 (COCH 3, s, 3H), 2.94 (BCH, d, J = 10.5 Hz, 1H). S11

12 (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] S12

13 Colorless oil, >99%, 97% ee, 7:1 dr. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.15 (CH 3, d, J = 6.9 Hz, 3H), 1.16 (CH 3, s, 6H), 1.20 (CH 3, s, 6H), 1.86 (COCH 3, s, 3H), 2.26 (CH 3, 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), (Ar-H, m, 3H). 13 C NMR (syn, 100 MHz, CDCl 3 ) 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, HRMS (ESI) m/z calcd for C 18 H 28 BO 3 ([M + H] + ): ; found: [α] 25 D 18.4 (c 1.00, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, anti- isomers mixture) = 18.4 min, t R (2, cis- isomer) = 22.2 min, t R (3, cis- isomer) = 26.5 min. For (S,R)-2d, the diagnostic peaks on 1 H NMR are: δ 2.21 (COCH 3, s, 3H), 2.96 (COCH, qd, J = 11.5 Hz, J = 7.4 Hz, 1H). S13

14 (3R,4R)-4-(3-Chlorophenyl)-3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-2 -one [(R,R)-2e, syn] Colorless oil, >99%, 93% ee, 16:1 dr. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.15 (CH 3, d, J = 6.9 Hz, 3H), 1.17 (CH 3, s, 6H), 1.20 (CH 3, s, 6H), 1.91 (COCH 3, s, 3H), 2.56 (BCH, d, J = 10.1 Hz, 1H), 3.05 (CH, qd, J = 10.1 Hz, J = 6.9 Hz, 1H), (Ar-H, m, 4H). 13 C NMR (syn, 100 MHz, CDCl 3 ) δ 16.6, 24.7, 29.1, 49.8, 83.7, 126.1, 127.4, 129.1, 129.7, 134.2, 142.8, HRMS (ESI) m/z calcd for C 17 H 25 BClO 3 ([M + H] + ): ; found: [α] 25 D 22.2 (c 1.20, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, anti- isomers mixture) = 19.7 min, t R (2, cis- isomer) = 24.3 min, t R (3, cis- isomer) = 30.1 min. For (S,R)-2e, the diagnostic peaks on 1 H NMR are: δ 2.20 (COCH 3, s, 3H), 2.94 (COCH, qd, J = 11.4 Hz, J = 7.3 Hz, 1H). S14

15 (3R,4R)-4-(3-Bromophenyl)-3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-2 S15

16 -one [(R,R)-2f, syn] Colorless oil, >99%, 95% ee, 13:1 dr. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.15 (CH 3, d, J = 7.3 Hz, 3H), 1.17 (CH 3, s, 6H), 1.20 (CH 3, s, 6H), 1.91 (COCH 3, s, 3H), 2.54 (BCH, d, J = 10.0 Hz, 1H), 3.04 (CH, qd, J = 10.0 Hz, J = 7.3 Hz, 1H), (Ar-H, m, 2H), (Ar-H, m, 1H), 7.35 (Ar-H, m, 1H). 13 C NMR (syn, 100 MHz, CDCl 3 ) δ 16.6, 24.7, 29.1, 49.9, 83.8, 122.5, 127.8, 129.0, 130.0, 132.0, 143.1, HRMS (ESI) m/z calcd for C 17 H 24 BBrNaO 3 ([M + Na] + ): ; found: [α] 25 D 19.7 (c 1.00, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, anti- isomers mixture) = 20.1 min, t R (2, cis- isomer) = 24.8 min, t R (3, cis- isomer) = 32.0 min. For (S,R)-2f, the diagnostic peaks on 1 H NMR are: δ 2.20 (COCH 3, s, 3H), 2.93 (COCH, qd, J = 11.0 Hz, J = 7.3 Hz, 1H). S16

17 (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] Colorless oil, >99%, 98% ee, 8:1 dr. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.15 (CH 3, d, J = 6.9 Hz, 3H), 1.16 (CH 3, s, 6H), 1.20 (CH 3, s, 6H), 1.85 (COCH 3, s, 3H), 2.25 (CH 3, s, 3H), 2.52 (BCH, d, J = 10.6 Hz, 1H), 3.05 (CH, qd, J = 10.6 Hz, J = 6.9 Hz, 1H), (Ar-H, m, 4H). 13 C NMR (syn, 100 MHz, CDCl 3 ) δ 16.7, 21.1, 24.6, 24.7, 29.1, 50.1, 83.5, 128.9, 129.2, 135.2, 137.3, HRMS (ESI) m/z calcd for C 18 H 28 BO 3 ([M + H] + ): ; found: [α] 25 D 19.9 (c 0.80, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, cis- isomer) = 26.1 min, t R (2, cis- isomer) = 29.6 min. For (S,R)-2g, the diagnostic peaks on 1 H NMR are: δ 2.20 (COCH 3, s, 3H), 2.93 (COCH, qd, J = 11.0 Hz, J = 7.3 Hz, 1H). S17

18 (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] S18

19 Colorless oil, >99%, 97% ee, 11:1 dr. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.14 (CH 3, d, J = 6.9 Hz, 3H), 1.16 (CH 3, s, 6H), 1.20 (CH 3, s, 6H), 1.85 (COCH 3, s, 3H), 2.50 (BCH, d, J = 10.1 Hz, 1H), 3.03 (CH, qd, J = 10.1 Hz, J = 6.9 Hz, 1H), 3.73 (OCH 3, s, 3H), (Ar-H, m, 2H), (Ar-H, m, 2H). 13 C NMR (syn, 100 MHz, CDCl 3 ) δ 16.7, 24.6, 24.7, 29.2, 50.1, 55.2, 83.5, 113.9, 130.0, 132.4, 157.7, HRMS (ESI) m/z calcd for C 18 H 28 BO 4 ([M + H] + ): ; found: [α] 25 D 34.8 (c 1.50, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak OD-H column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, anti- isomer) = 27.8 min, t R (2, anti- isomer) = 29.5 min, t R (3, cis- isomer) = 30.7 min, t R (4, cis- isomer) = 35.1 min. For (S,R)-2h, the diagnostic peaks on 1 H NMR are: δ 2.19 (COCH 3, s, 3H), 2.90 (COCH, qd, J = 11.0 Hz, J = 7.3 Hz, 1H). S19

20 (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] Colorless oil, >99%, 96% ee, 12:1 dr. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.15 (CH 3, d, J = 6.8 Hz, 3H), 1.16 (CH 3, s, 6H), 1.20 (CH 3, s, 6H), 1.87 (COCH 3, s, 3H), 2.55 (BCH, d, J = 10.1 Hz, 1H), 3.04 (CH, qd, J = 10.1 Hz, J = 6.8 Hz, 1H), (Ar-H, m, 2H), (Ar-H, m, 2H). 13 C NMR (syn, 100 MHz, CDCl 3 ) δ 16.7, 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, HRMS (ESI) m/z calcd for C 17 H 25 BFO 3 ([M + H] + ): ; found: [α] 25 D 38.9 (c 1.60, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, anti- isomers mixture) = 19.4 min, t R (2, cis- isomer) = 23.2 min, t R (3, cis- isomer) = 30.8 min. For (S,R)-2i, the diagnostic peaks on 1 H NMR are: δ 2.20 (COCH 3, s, 3H), 2.91 (COCH, qd, J = 11.0 Hz, J = 7.4 Hz, 1H). S20

21 (3R,4R)-4-(4-Chlorophenyl)-3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)butan-2 -one [(R,R)-2j, syn] S21

22 Colorless oil, >99%, 97% ee, 10:1 dr. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.15 (CH 3, d, J = 6.9 Hz, 3H), 1.16 (CH 3, s, 6H), 1.20 (CH 3, s, 6H), 1.89 (COCH 3, s, 3H), 2.55 (BCH, d, J = 10.1 Hz, 1H), 3.05 (CH, qd, J = 10.1 Hz, J = 6.9 Hz, 1H), (Ar-H, m, 2H), (Ar-H, m, 2H). 13 C NMR (syn, 100 MHz, CDCl 3 ) δ 16.7, 24.6, 24.7, 29.1, 49.9, 83.7, 128.6, 130.4, 131.6, 139.2, HRMS (ESI) m/z calcd for C 17 H 25 BClO 3 ([M + H] + ): ; found: [α] 25 D 10.5 (c 0.80, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, anti- isomers mixture) = 20.6 min, t R (2, cis- isomer) = 25.1 min, t R (3, cis- isomer) = 31.6 min. For (S,R)-2j, the diagnostic peaks on 1 H NMR are: δ 2.20 (COCH 3, s, 3H), 2.92 (COCH, qd, J = 11.5 Hz, J = 7.3 Hz, 1H). S22

23 (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] Colorless oil, >99%, 93% ee, 11:1 dr. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.15 (CH 3, d, J = 6.9 Hz, 3H), 1.16 (CH 3, s, 6H), 1.19 (CH 3, s, 6H), 1.89 (COCH 3, s, 3H), 2.54 (BCH, d, J = 10.0 Hz, 1H), 3.05 (CH, qd, J = 10.0 Hz, J = 6.9 Hz, 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, CDCl 3 ) δ 16.7, 24.6, 24.7, 29.1, 49.8, 83.7, 119.7, 130.8, 131.5, 139.7, HRMS (ESI) m/z calcd for C 17 H 25 BBrO 3 ([M + H] + ): ; found: [α] 25 D 14.3 (c 0.60, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, anti- isomers mixture) = 20.0 min, t R (2, cis- isomer) = 24.9 min, t R (3, cis- isomer) = 30.4 min. S23

24 (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] S24

25 White solid. 1 H NMR (anti, 400 MHz, CDCl 3 ) δ 0.97 (CH 3, d, J = 7.4 Hz, 3H), 1.09 (CH 3, s, 6H), 1.16 (CH 3, s, 6H), 2.20 (COCH 3, s, 3H), 2.22 (BCH, d, J = 11.0 Hz, 1H), 2.92 (CH, qd, J = 11.0 Hz, J = 7.4 Hz, 1H), 7.04 (Ar-H, d, J = 8.2 Hz, 2H), 7.35 (Ar-H, d, J = 8.3 Hz, 2H). 13 C NMR (syn, 100 MHz, CDCl 3 ) δ 16.2, 24.5, 24.6, 28.0, 50.7, 83.5, 119.5, 130.7, 131.6, 140.0, [α] 25 D 22.0 (c 0.30, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AD column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, anti- isomer) = 24.1 min, t R (2, anti- isomer) = 28.9 min, t R (3, cis- isomers mixture) = 29.4 min. S25

26 (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. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.14 (CH 3, s, 6H), 1.21 (CH 3, s, 6H), 1.24 (CH 3, d, J = 7.4 Hz, 3H), 1.87 (COCH 3, s, 3H), 3.26 (CH, qd, J = 9.2 Hz, J = 7.4 Hz, 1H), 3.46 (BCH, d, J = 9.2 Hz, 1H), (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, CDCl 3 ) 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, HRMS (ESI) m/z calcd for C 21 H 28 BO 3 ([M + H] + ): ; found: [α] 25 D 30.6 (c 1.50, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak OD-H column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, anti- isomer) = 26.0 min, t R (2, cis- isomer and anti- isomer) = 30.5 min, t R (3, cis- isomer) = 36.2 min. For (S,R)-2l, the diagnostic peak on 1 H NMR is: δ 2.27 (COCH 3, s, 3H). S26

27 (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] S27

28 White solid, 95%, 79% ee, 15:1 dr. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.16 (CH 3, s, 6H), 1.21 (CH 3, s, 6H), 1.21 (CH 3, d, J = 6.9 Hz, 3H), 1.85 (COCH 3, s, 3H), 2.75 (BCH, d, J = 10.5 Hz, 1H), 3.22 (CH, qd, J = 10.5 Hz, J = 6.9 Hz, 1H), (Ar-H, m, 3H), 7.62 (Ar-H, s, 1H), (Ar-H, m, 3H). 13 C NMR (syn, 100 MHz, CDCl 3 ) 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, HRMS (ESI) m/z calcd for C 21 H 28 BO 3 ([M + H] + ): ; found: [α] 25 D 16.3 (c 1.50, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, anti- isomers mixture) = 22.5 min, t R (2, cis- isomer) = 31.5 min, t R (3, cis- isomer) = 46.4 min. For (S,R)-2l, the diagnostic peaks on 1 H NMR are: δ 2.24 (COCH 3, s, 3H), 2.45 (BCH, d, J = 11.5 Hz, 1H), 3.10 (CH, qd, J = 11.5 Hz, J = 7.4 Hz, 1H). S28

29 (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. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 0.87 (CH 3, t, J = 7.3 Hz, 3H), 1.14 (CH 3, s, 6H), 1.18 (CH 3, s, 6H), (CH 2, m, 2H), 1.75 (COCH 3, 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), (Ar-H, m, 1H), (Ar-H, m, 4H). 13 C NMR (syn, 100 MHz, CDCl 3 ) 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, HRMS (ESI) m/z calcd for C 18 H 28 BO 3 ([M + H] + ): ; found: [α] 25 D 18.2 (c 0.50, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, anti- isomers mixture) = 18.5 min, t R (2, cis- isomer) = 23.6 min, t R (3, cis- isomer) = 28.5 min. S29

30 (S)-3-((R)-phenyl(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)pentan-2-one [(S,R)-2n, syn] S30

31 Colorless oil, 93% ee. 1 H NMR (anti, 400 MHz, CDCl 3 ) δ 0.70 (CH 3, t, J = 7.4 Hz, 3H), 1.08 (CH 3, s, 6H), 1.16 (CH 3, s, 6H), (CH 2, m, 1H), (CH 2, m, 1H), 2.20 (COCH 3, 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), (Ar-H, m, 5H). 13 C NMR (syn, 100 MHz, CDCl 3 ) δ 9.6, 22.1, 24.4, 24.6, 29.1, 56.3, 83.3, 125.6, 128.5, 129.0, 140.6, HRMS (ESI) m/z calcd for C 18 H 28 BO 3 ([M + H] + ): ; found: [α] 25 D 46.3 (c 0.60, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AD column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, anti- isomer) = 20.5 min, t R (2, anti- isomer) = 22.8 min, t R (3, cis- isomers mixture) = 25.8 min. S31

32 (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. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 0.76 (CH 3, t, J = 7.3 Hz, 3H), 1.14 (CH 3, d, J = 6.9 Hz, 3H), 1.16 (CH 3, s, 6H), 1.21 (CH 3, s, 6H), 1.92 (COCH 2, qd, J = 17.9 Hz, J = 7.3 Hz, 1H), 2.24 (COCH 2, 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), (Ar-H, m, 1H), (Ar-H, m, 4H). 13 C NMR (syn, 100 MHz, CDCl 3 ) δ 7.4, 17.1, 24.6, 24.7, 35.7, 49.1, 83.6, 125.8, 128.4, 129.1, 140.6, HRMS (ESI) m/z calcd for C 18 H 28 BO 3 ([M + H] + ): ; found: [α] 25 D 30.5 (c 0.80, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AD column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, anti- isomer) = 21.3 min, t R (2, cis- isomer) = 24.3 min, t R (3, cis- isomer and anti- isomer) = 28.1 min. For (S,R)-2o, the diagnostic peaks on 1 H NMR are: δ 2.32 (BCH, d, J = 11.4 Hz, 1H), 2.54 (COCH 2, q, J = 7.3 Hz, 2H), 2.97 (COCH, qd, J = 11.4 Hz, J = 6.9 Hz, 1H). S32

33 (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] S33

34 Colorless oil, 89%, 90% ee, 14:1 dr. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.20 (CH 3, s, 6H), 1.24 (CH 3, s, 6H), 1.28 (CH 3, 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), (Ar-H, m, 8H), (Ar-H, m, 2H). 13 C NMR (syn, 100 MHz, CDCl 3 ) 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, HRMS (ESI) m/z calcd for C 22 H 28 BO 3 ([M + H] + ): ; found: [α] 25 D 28.7 (c 0.60, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, anti- isomers mixture) = 21.3 min, t R (2, cis- isomer) = 25.2 min, t R (3, cis- isomer) = 28.5 min. For (S,R)-2p, the diagnostic peaks on 1 H 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). S34

35 (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. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 0.92 (CH 3, d, J = 7.3 Hz, 3H), 1.18 (CH 3, d, J = 6.9 Hz, 3H), 1.24 (CH 3, s, 6H), 1.25 (CH 3, 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 (OCH 3, s, 3H), (Ar-H, m, 2H), (Ar-H, m, 2H). 13 C NMR (syn, 100 MHz, CDCl 3 ) δ 14.0, 17.6, 24.7, 24.9, 43.2, 55.5, 83.0, 113.7, 130.2, 130.7, 163.3, HRMS (ESI) m/z calcd for C 18 H 28 BO 4 ([M + H] + ): ; found: [α] 25 D 59.2 (c 0.50, CH 2 Cl 2 ).The enantiomeric excess was determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, cis- isomer) = 34.0 min, t R (2, cis- isomer) = 62.2 min. For (S,R)-2q, the diagnostic peaks on 1 H NMR are: δ 1.20 (CH 3, d, J = 6.8 Hz, 3H), 3.84 (OCH 3, s, 3H). S35

36 (R)-2-((R)-Phenyl(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)cyclohexanone [(R,R)-2r, syn] S36

37 Colorless oil, >99%, 79% ee, 12:1 dr. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.19 (CH 3, s, 6H), 1.23 (CH 3, s, 6H), (CH 2, m, 3H), (CH 2, m, 3H), (COCH 2, m, 2H), 2.68 (BCH, d, J = 6.2 Hz, 1H), (COCH, m, 1H), (Ar-H, m, 5H). 13 C NMR (syn, 100 MHz, CDCl 3 ) δ 24.7, 24.8, 25.2, 27.9, 31.8, 41.9, 54.5, 83.3, 125.6, 128.2, 130.1, 140.9, HRMS (ESI) m/z calcd for C 19 H 28 BO 3 ([M + H] + ): ; found: [α] 25 D 9.8 (c 0.60, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AD column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, cis- isomer) = 31.8 min, t R (2, cis- isomer) = 36.3 min. For (S,R)-2r, the diagnostic peak on 1 H NMR is: δ 2.17 (BCH, d, J = 11.4 Hz, 1H). S37

38 (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. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.23 (CH 3, s, 6H), 1.25 (CH 3, s, 6H), 1.95 (COCH 3, s, 3H), 2.92 (BCH, d, J = 5.0 Hz, 1H), 3.63 (OCH 3, s, 3H), 5.00 (NCH, dd, J = 8.7 Hz, J = 5.0 Hz, 1H), 6.35 (NH, d, J = 8.7 Hz, 1H), (Ar-H, m, 5H). 13 C NMR (syn, 100 MHz, CDCl 3 ) δ 23.4, 24.6, 24.9, 52.2, 54.8, 84.2, 126.7, 128.6, 129.4, 137.6, 169.8, HRMS (ESI) m/z calcd for C 18 H 27 BNO 5 ([M + H] + ): ; found: [α] 25 D (c 1.20, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/ i PrOH (90:10); flow rate = 1.0 ml/min; t R (1, anti- isomer) = 17.2 min, t R (2, anti- isomer) = 24.8 min, t R (3, cis- isomer) = 29.0 min, t R (4, cis- isomer) = 55.4 min. For (S,S)-4a, the diagnostic peaks on 1 H NMR are: δ 1.16 (CH 3, s, 6H), 1.18 (CH 3, s, 6H), 1.82 (COCH 3, s, 3H), 2.78 (BCH, d, J = 9.2 Hz, 1H), 3.68 (OCH 3, 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, S38

39 (2R,3S)-Benzyl S39

40 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. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.16 (CH 3, s, 6H), 1.19 (CH 3, s, 6H), 1.95 (COCH 3, s, 3H), 2.93 (BCH, d, J = 5.5 Hz, 1H), (NCH, PhCH 2, m, 3H), 6.39 (NH, d, J = 8.7 Hz, 1H), (Ar-H, m, 7H), (Ar-H, m, 3H). 13 C NMR (syn, 100 MHz, CDCl 3 ) δ 23.3, 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, HRMS (ESI) m/z calcd for C 24 H 31 BNO 5 ([M + H] + ): ; found: [α] 25 D (c 0.70, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak OD-H column: eluent, hexanes/ i PrOH (90:10); flow rate = 0.5 ml/min; t R (1, cis- isomer) = 27.9 min, t R (2, cis- isomer) = 30.7 min. S40

41 (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. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.12 (CH 3, s, 6H), 1.15 (CH 3, s, 6H), 1.83 (COCH 3, s, 3H), 2.84 (BCH, d, J = 8.7 Hz, 1H), (NCH, PhCH 2, m, 3H), 5.73 (NH, d, J = 8.2 Hz, 1H), (Ar-H, m, 5H), (Ar-H, m, 5H). 13 C NMR (syn, 100 MHz, CDCl 3 ) δ 23.1, 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, HRMS (ESI) m/z calcd for C 24 H 31 BNO 5 ([M + H] + ): ; found: [α] 25 D (c 1.00, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak OD-H column: eluent, hexanes/ i PrOH (90:10); flow rate = 1.0 ml/min; t R (1, cis- isomer) = 17.2 min, t R (2, cis- isomer) = 21.3 min. S41

42 (2R,3S)-Isopropyl 2-acetamido-3-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)propanoate [(R,S)-4c, S42

43 syn] Colorless oil, >99%, 98% ee, 3.3:1 dr. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.05 (CH 3, d, J = 6.4 Hz, 3H), 1.17 (CH 3, d, J = 6.0 Hz, 3H), 1.22 (CH 3, s, 6H), 1.24 (CH 3, s, 6H), 1.96 (COCH 3, s, 3H), 2.87 (BCH, d, J = 6.0 Hz, 1H), (NCH, CHMe 2, m, 2H), 6.35 (NH, d, J = 8.7 Hz, 1H), (Ar-H, m, 5H). 13 C NMR (syn, 100 MHz, CDCl 3 ) 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, HRMS (ESI) m/z calcd for C 20 H 31 BNO 5 ([M + H] + ): ; found: [α] 25 D (c 1.20, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak OD-H column: eluent, hexanes/ i PrOH (90:10); flow rate = 0.5 ml/min; t R (1, cis- isomer) = 19.6 min, t R (2, cis- isomer) = 22.1 min, t R (3, anti- isomer) = 27.8 min, t R (4, anti- isomer) = 34.5 min. For (S,S)-4c, the diagnostic peaks on 1 H NMR are: δ 1.86 (COCH 3, s, 3H), 2.83 (BCH, d, J = 8.2 Hz, 1H). S43

44 (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. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.21 (CH 3, s, 6H), 1.23 (CH 3, s, 6H), 1.30 (C(CH 3 ) 3, s, 9H), 1.96 (COCH 3, 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), (Ar-H, m, 5H). 13 C NMR (syn, 100 MHz, CDCl 3 ) δ 23.4, 24.7, 24.9, 27.9, 55.2, 81.8, 84.2, 126.4, 128.5, 129.4, 138.0, 169.6, HRMS (ESI) m/z calcd for C 21 H 33 BNO 5 ([M + H] + ): ; found: [α] 25 D +4.5 (c 1.20, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak OD-H column: eluent, hexanes/ i PrOH (90:10); flow rate = 0.5 ml/min; t R (1, cis- isomer) = 17.7 min, t R (2, cis- isomer) = 22.7 min. For (S,S)-4c, the diagnostic peaks on 1 H NMR are: δ 1.85 (COCH 3, 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). S44

45 (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] S45

46 Colorless oil, 89%, 94% ee, 4.9:1 dr. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.20 (CH 3, s, 6H), 1.22 (CH 3, s, 6H), 1.98 (COCH 3, s, 3H), 2.70 (BCH, d, J = 9.6 Hz, 1H), 3.35 (OCH 3, s, 1H), 3.96 (COCH, d, J = 9.6 Hz, 1H), (Ar-H, m, 5H). 13 C NMR (syn, 100 MHz, CDCl 3 ) δ 24.5, 24.8, 25.6, 58.4, 83.8, 89.8, 126.4, 128.6, 129.3, 136.9, HRMS (ESI) m/z calcd for C 17 H 26 BO 4 ([M + H] + ): ; found: [α] 25 D 9.5 (c 0.40, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, anti- isomer) = 29.7 min, t R (2, anti- isomer) = 32.1 min, t R (3, cis- isomer) = 35.5 min, t R (4, cis- isomer) = 38.5 min. For (S,S)-6, the diagnostic peaks on 1 H NMR are: δ 2.12 (COCH 3, s, 3H), 3.18 (OCH 3, s, 1H), 4.14 (COCH, d, J = 9.6 Hz, 1H). S46

47 (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. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.17 (CH 3, s, 6H), 1.20 (CH 3, s, 6H), 2.07 (COCH 3, s, 3H), 3.02 (BCH, d, J = 11.2 Hz, 1H), 4.64 (COCH, d, J = 11.2 Hz, 1H), (Ar-H, m, 5H). For (S,S)-8, the diagnostic peak on 1 H 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). i PrOH (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 S47

48 acetate. The organic layer was washed with saturated NaHCO 3 for three times and the water layer was extracted with ethyl acetate. The combined organic layer was washed with brine and dried over Na 2 SO 4. The crude product was concentrated and analyzed by 1 H 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. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 2.25 (COCH 3, 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), (Ar-H, m, 5H). 13 C NMR (syn, 100 MHz, CDCl 3 ) δ 28.5, 68.5, 73.7, 126.5, 128.7, 128.7, 138.8, [α] 25 D (c 0.30, CH 2 Cl 2 ). The enantiomeric excess was determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, syn- isomer) = 45.8 min, t R (2, syn- isomer) = 57.8 min. For (S,S)-9, the diagnostic peaks on 1 H NMR are: δ 2.33 (COCH 3, 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). S48

49 Procedure: To a solution of syn-2a (80 mg, 0.28 mmol, 93% ee, 50:1 dr) in THF (2 ml) and H 2 O (2 ml) was added NaBO 3.4H 2 O (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 NaHCO 3 for three times. The water layer was extracted with ethyl acetate. The combined organic layer was washed with brine and dried over Na 2 SO 4. The crude product was concentrated and analyzed by 1 H 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. 1 H NMR (syn, 400 MHz, CDCl 3 ) δ 1.07 (CH 3, d, J = 7.3 Hz, 3H), 2.14 (COCH 3, 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), (Ar-H, m, 5H). [α] 25 D (c 0.20, CH 2 Cl 2 ). The enantiomeric excess S49

50 was determined by HPLC with a Chiralpak AS-H column: eluent, hexanes/ i PrOH (99:1); flow rate = 0.5 ml/min; t R (1, syn- isomer) = 36.4 min, t R (2, anti- isomer) = 40.7 min, (3, syn- isomer) = 46.8 min, t R (4, anti- isomer) = 52.3 min. For (S,R)-12, the diagnostic peaks on 1 H NMR are: δ 0.92 (CH 3, d, J = 7.4 Hz, 3H), 2.20 (COCH 3, 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 Bu 4 NBH 4 (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 Na 2 CO 3 twice and then washed with brine. The extract was dried over Na 2 SO 4. The crude product was concentrated and analyzed by 1 H NMR. (1R,2S,3S)-2-Methyl-1-phenylbutane-1,3-diol (anti diol 13) S50

51 Colorless oil, ~80%. 1 H NMR (400 MHz, CDCl 3 ) δ 0.79 (CH 3, d, J = 6.9 Hz, 3H), 1.28 (CH 3, d, J = 6.4 Hz, 3H), (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), (Ar-H, m, 5H). [α] 25 D (c 0.80, CH 2 Cl 2 ). 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 NaHCO 3 and brine. The extract was dried over Na 2 SO 4. The crude product was concentrated and analyzed by 1 H NMR. Colorless oil, ~95%. 1 H NMR (400 MHz, CDCl 3 ) δ 0.81 (CH 3, d, J = 6.9 Hz, 3H), 1.21 (CH 3, d, J = 6.4 Hz, 3H), (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), (Ar-H, m, 5H). [α] 25 D (c 0.80, CH 2 Cl 2 ). D) Equilibrium experiment with (R,R)-2a Procedure: To a dry 10 ml Schlenk tube was added syn-2a (20 mg, mmol) in THF (0.5 ml). under argon atmosphere. NaO t Bu (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 S51

52 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 NaHCO 3 and brine. The extract was dried over Na 2 SO 4. The crude product was concentrated and analyzed by 1 H NMR. The mixture was then purified by flash chromatography and analyzed by HPLC. S52

53 HPLC Traces (R,R)-2a S53

54 (S,R)-2a (S,R)-isomer + (S,S)-isomer (R,S)-isomer (R,R)-isomer S54

55 (R,R)-2b (S,R)-isomer + (R,S)-isomer (R,R)-isomer (S,S)-isomer S55

56 (R,R)-2c S56

57 (R,R)-2d S57

58 (R,R)-2e S58

59 (R,R)-2f S59

60 (R,R)-2g S60

61 (R,R)-2h S61

62 (R,R)-2i S62

63 (R,R)-2j S63

64 (R,R)-2k S64

65 (S,R)-2k (S,R)-isomer (R,S)-isomer syn-isomers S65

66 (R,R)-2l (R,R)-isomer + one anti isomer One anti isomer (S,S)-isomer S66

67 (R,R)-2m S67

68 (R,R)-2n S68

69 (S,R)-2n S69

70 (R,R)-2o (R,R)-isomer + one anti isomer One anti isomer (S,S)-isomer S70

71 (R,R)-2p S71

72 (R,S)-2q S72

73 (R,R)-2r S73

74 (R,S)-4a anti -isomers syn -isomers S74

75 (R,S)-4b S75

76 (S,S)-4b S76

77 (R,S)-4c S77

78 (R,S)-4d S78

79 (R,S)-6 Include an impurity S79

80 (R,S)-9 S80

81 (R,R)-12 Include an impurity S81

82 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 = 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 P space group. However, multiple attempts to solve the structure were unsuccessful. The Bravais lattice was then lowered to monoclinic with a β angle of 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 P2 1 with the twin law and a BASF of Hydrogen atoms bonded to carbon atoms were geometrically constrained using the appropriate AFIX commands. S82

83 Crystal data and structure refinement for (S,R)-2k. Identification code Crystal Color Crystal Habit Empirical formula li14_06 colorless blade C17 H24 B Br O3 Formula weight Temperature Wavelength Crystal system 100(2) K A Monoclinic Space group P2 1 Unit cell dimensions a = (2) Å alpha = 90. b = (3) Å beta = (3). c = (3) Å gamma = 90. Volume (7) Å 3 Z 4 Calculated density Mg/m 3 Absorption coefficient mm -1 F(000) 760 Crystal size x x mm Theta range for data collection to Limiting indices -13<=h<=13, -15<=k<=16, -18<=l<=18 Reflections collected / unique / 8402 [R(int) = ] Completeness to theta = % Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 8402 / 1 / 398 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Largest diff. peak and hole and e. A -3 S83

84 Atomic coordinates ( x 10 4 ) 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) S84

85 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) S85

86 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) S86

87 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) S87

88 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: S88

89 Anisotropic displacement parameters (Å 2 x 10 3 ) for li14_06. The anisotropic displacement factor exponent takes the form: -2 π 2 [ h 2 a* 2 U 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) S89