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1 Supporting Information Copper-Catalyzed Enantioselective Allylic Substitution with Alkylboranes Yoshinori Shido, Mika Yoshida, Masahito Tanabe, Hirohisa hmiya,* and Masaya Sawamura* Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo , Japan Table of Contents Instrumentation and Chemicals Preparation of Allylic Chlorides Characterization Data for Allylic Chlorides Procedures for Copper-Catalyzed Enantioselective Allylic Substitution Characterization Data for Allylic Substitution Products Ligand Effects References NMR Spectra S1 S2 S2 S3 S4 S4 S5 S5 S11 S12 S12 S13 S52 Instrumentation and Chemicals NMR spectra were recorded on a Varian Gemini 2000 spectrometer, operating at 300 MHz for 1 H NMR and 75.4 MHz for 13 C NMR. Chemical shift values for 1 H and 13 C are referenced to Me 4 Si and the residual solvent resonances, respectively. Chemical shifts are reported in ppm. Mass spectra were obtained with Thermo Fisher Scientific Exactive, JEL JMS-T100LP or JEL JMS-700TZ at the Instrumental Analysis Division, Equipment Management Center, Creative Research Institution, Hokkaido University. Elemental analysis was performed at the Instrumental Analysis Division, Equipment Management Center, Creative Research Institution, Hokkaido University. HPLC analyses were conducted on a HITACHI ELITE LaChrom system with a HITACHI L-2455 diode array detector. IR spectra were recorded on a Perkin-Elmer Spectrum ne. TLC analyses were performed on commercial glass plates bearing 0.25-mm layer of Merck Silica gel 60F 254. Silica gel (Kanto Chemical Co., Silica gel 60 N, spherical, neutral) was used for column chromatography. Gas chromatographic (GLC) analyses were conducted on a Shimadzu GC-14B equipped with a flame ionization detector. Gel permeation chromatography (GPC) was performed by LC-908 (Japan Analytical Industry Ltd., two in-line JAIGEL-2H, CHCl 3, 3.5 ml/min, UV and RI detectors). All reactions were carried out under nitrogen or argon atmosphere. Materials were obtained from commercial suppliers or prepared according to standard procedures unless otherwise noted. 9-Borabicyclo[3,3,1]nonane dimer (9-BBN-H) 2, (CuTf) 2 toluene and MeK were purchased from Aldrich Chemical Co., stored under nitrogen, and used as it is. (R)-DTBM-SEGPHS was S1

2 purchased from Strem Chemicals Inc., stored under nitrogen, and used as it is. Dichloromethane (DCM) was purchased from Kanto Chemical Co., stored over 4Å molecular sieves under nitrogen. 1,4-Dioxane was purchased from Kanto Chemical Co., distilled from sodium/benzophenone and stored over 4Å molecular sieves under nitrogen. Alkenes 1a h and allylic chloride 3d 1 are well known compounds. Preparation of Allylic Chlorides Preparation of (Z)-Allylic Chlorides 3a c, e and f. Addition of the lithium acetylides to formaldehyde gave the corresponding propargylic alcohols. Next, Lindlar reduction followed by chlorination afforded the allylic chlorides 3a c, e and f. The preparation of 3a is representative (Scheme S1). Scheme S1 Ph H H 2 (1 atm) Pd CaC 3 (50 mg/g) quinoline (10 ul/mg) hexane/acetone (5:1) rt, 3 h 1) n-buli (1.1 eq) Et 2, 78 C, 0.5 h 2) (HCH) n (2 eq) 78 C to rt, 12 h 97% Ph H Ph NCS (1.1 eq) PPh 3 (1.2 eq) DCM 0 C to rt, 2 h 71% in 2 steps H Ph Cl Preparation of (Z)-1-Dimethylphenysilyl-3-chloro-1-pentene (3g) (Scheme S2). THP-protection of commercially available propargyl alcohol followed by silylation gave -silylated propargylic alcohol derivative. Next, DIBAL-H reduction followed by deprotection afforded -silylated allylic alcohol. Finally, allylic substrates were prepared by chlorination of the -silylated allylic alcohol. Scheme S2 p-tsh (2.5 mol%) DHP (1.2 eq) H CH 2 Cl 2 0 C to rt, 2 h 1) n-buli (1.05 eq) THF, 78 C, 0.5 h PhMe 2 Si THP 2) PhMe 2 SiCl (1.1 eq) 78 C to rt, 12 h 91% in 2 steps THP DIBAL-H (1.2 eq) Et 2 0 C to rt, 24 h PhMe 2 Si p-tsh (2.5 mol%) PhMe 2 Si NCS (1.1 eq) PPh 3 (1.2 eq) PhMe 2 Si THP MeH 0 C to rt, 3 h 83% in 2 steps H CH 2 Cl 2 0 C to rt, 2 h 80% Cl S2

3 Characterization Data for Allylic Chlorides (Z)-(5-Chloro-3-penten-1-yl)benzene (3a) Ph Colorless il. IR (neat) 697, 742, 1250, 1453, 1496, 1652, 2931, 3027 cm 1. 1 H NMR (300 MHz, CDCl 3 ) (m, 2H), 2.71 (t, J = 7.2 Hz, 2H), (m, 2H), (m, 2H), (m, 3H), (m, 2H). 13 C NMR (75.4 MHz, CDCl 3 ) 28.86, 35.32, 39.22, , , , , , HRMS EI (m/z): [M] + calcd for C 11 H 13 Cl, ; found, Cl (Z)-1-Chloro-2-heptene (3b) Colorless il. IR (neat) 756, 1250, 1458, 1652, 2930 cm 1. 1 H NMR (300 MHz, CDCl 3 ) 0.91 (t, J = 7.2 Hz, 3H), (m, 4H), (m, 2H), 4.10 (d, J = 4.5 Hz, 2H), (m, 2H). 13 C NMR (75.4 MHz, CDCl 3 ) 13.76, 22.15, 26.68, 31.32, 39.48, , HRMS EI (m/z): [M] + calcd for C 7 H 13 Cl, ; found, Cl (Z)-1,7-Dichloro-2-heptene (3c) Cl 2 Colorless il. IR (neat) 756, 1251, 1454, 1652, 2941 cm 1. 1 H NMR (300 MHz, CDCl 3 ) (m, 2H), (m, 2H), (m, 2H), 3.55 (t, J = 6.6 Hz, 2H), 4.09 (d, J = 7.2 Hz, 2H), (m, 2H). 13 C NMR (75.4 MHz, CDCl 3 ) 26.17, 26.31, 31.85, 39.21, 44.71, , HRMS EI (m/z): [M] + calcd for C 7 H 12 Cl 2, ; found, Cl (Z)-(3-Chloro-1-propen-1-yl)cyclohexane (3e) Colorless il. IR (neat) 766, 890, 1249, 1448, 1651, 2850, 2924 cm 1. 1 H NMR (300 MHz, CDCl 3 ) (m, 5H), (m, 5H), (m, 1H), 4.11 (d, J = 7.2 Hz, 2H), (m, 2H). 13 C NMR (75.4 MHz, CDCl 3 ) 25.57, 25.73, 32.90, 36.24, 39.80, , HRMS EI (m/z): [M] + calcd for C 9 H 15 Cl, ; found, Cl (Z)-tert-Butyl[(7-chloro-5-hepten-1-yl)oxy]dimethylsilane (3f) TBS 3 Cl S3

4 Colorless il. IR (neat) 773, 833, 1097, 1252, 1472, 2858, 2930 cm 1. 1 H NMR (300 MHz, CDCl 3 ) 0.05 (s, 3H), 0.06 (s, 3H), 0.89 (s, 9H), (m, 4H), (m, 2H), 3.62 (t, J = 6.0 Hz, 2H), 4.10 (d, J = 6.6 Hz, 2H), (m, 2H). 13 C NMR (75.4 MHz, CDCl 3 ) 5.46, 18.23, 25.49, 25.85, 26.74, 32.20, 39.42, 62.84, , HRMS EI (m/z): [M Cl] + calcd for C 13 H 27 Si, ; found, (Z)-1-Dimethylphenysilyl-3-chloro-1-pentene (3g) PhMe 2 Si Cl Colorless il. IR (neat) 698, 782, 818, 1111, 1250, 1427, 1604, 2958 cm 1. 1 H NMR (300 MHz, CDCl 3 ) 0.42 (s, 6H), 3.95 (d, J = 7.8 Hz, 2H), 5.92 (d, J = 14.1 Hz, 1H), 6.51 (dt J = 14.1, 7.8 Hz, 1H), (m, 3H), (m, 2H). 13 C NMR (75.4 MHz, CDCl 3 ) 1.24, 43.82, , , , , , HRMS EI (m/z): [M CH 3 ] + calcd for C 10 H 12 ClSi, ; found, Procedures for Copper-Catalyzed Enantioselective Allylic Substitution with Alkylboranes Typical Procedure for Copper-Catalyzed Enantioselective Allylic Substitution with Alkylboranes (Table 2, entry 1). 2-(3-Buten-1-yl)-1,3-dioxane (1b) (196.6 L, 1.3 mmol) and (9-BBN-H) 2 (151.2 mg, mmol) were placed in a vial containing a magnetic stirring bar. The vial was sealed with a Teflon -coated silicon rubber septum and the vial was evacuated and filled with argon. 1,4-Dioxane (1.0 ml) was added to the vial, and then the mixture was stirred at 60 C for 1 h to prepare an alkylborane. n the other hand, (CuTf) 2 toluene (26 mg, 0.05 mmol), (R)-DTBM-SEGPHS (118 mg, 0.1 mmol) and MeK (77 mg, 1.1 mmol) were placed in another vial. The vial was sealed with a Teflon -coated silicon rubber septum and the vial was evacuated and filled with argon. After DCM (3.0 ml) was added to the vial, the mixture was stirred at 25 C for 1 h. Next, the alkylborane solution was transferred to the vial containing a Cu(I) (R)-DTBM-SEGPHS complex. Then, allylic chloride 3b (132.6 mg, 1.0 mmol) was added. After 72 h stirring at 15 C, diethyl ether was added to the mixture. The mixture was filtered through a short plug of silica gel, which was then washed with diethyl ether. After the solvent was removed under reduced pressure, flash chromatography on silica gel (0 5% EtAc/hexane) provided 4bb (223.6 mg, 0.93 mmol) in 93% yield. Typical Procedure for Synthesis of Chiral Allylsilanes (Table 3, entry 5). 6-Chloro-1-hexene (1i) (172 L, 1.3 mmol) and (9-BBN-H) 2 (151.2 mg, mmol) were placed in a vial containing a magnetic stirring bar. The vial was sealed with a Teflon -coated silicon rubber septum and the vial was evacuated and filled with argon. 1,4-Dioxane (1.0 ml) was added to the vial, and then the mixture was stirred at 60 C for 1 h to prepare an alkylborane. n the other hand, (CuTf) 2 toluene (26 mg, 0.05 mmol), (R)-DTBM-SEGPHS (118 mg, 0.1 mmol) and MeK (77 mg, 1.1 mmol) were placed in another vial. The vial was sealed with a Teflon -coated silicon rubber septum and S4

5 the vial was evacuated and filled with argon. After DCM (3.0 ml) was added to the vial, the mixture was stirred at 25 C for 1 h. Next, the alkylborane solution was transferred to the vial containing a Cu(I) (R)-DTBM-SEGPHS complex. Then, allylic chloride 3g (211 mg, 1.0 mmol) was added. After 48 h stirring at 15 C, diethyl ether was added to the mixture. The mixture was filtered through a short plug of silica gel, which was then washed with diethyl ether. After the solvent was removed under reduced pressure, flash chromatography on silica gel (hexane) provided 4ig (259.5 mg, 0.88 mmol) in 88% yield. Characterization Data for Allylic Substitution Products (S)-1,2-Dimethoxy-4-(4-phenethyl-5-hexen-1-yl)benzene (4aa) Me Ph Me The product 4aa was purified by flash chromatography on silica gel (0 10% EtAc/hexane) followed by GPC (CHCl 3 ) [59% isolated yield from (Z)-3a]. Colorless il. IR (neat) 699, 749, 1030, 1140, 1235, 1515, 1591, 2932 cm 1. 1 H NMR (300 MHz, CDCl 3 ) (m, 6H), (m, 1H), (m, 2H), (m, 2H), 3.85 (s, 3H), 3.86 (s, 3H), (m, 2H), 5.57 (dt, J = 17.1, 9.6 Hz, 1H), 6.69 (d, J = 6.6 Hz, 2H), 6.78 (d, J = 8.7 Hz, 1H), (m, 3H), (m, 2H). 13 C NMR (75.4 MHz, CDCl 3 ) 29.09, 33.39, 34.50, 35.45, 36.71, 43.55, 55.70, 55.82, , , , , , , , , , , , HRMS EI (m/z): [M] + calcd for C 22 H 28 2, ; found, [ ] 25 D 0.75 (77% ee, c 1.03, CHCl 3 ). HPLC analysis [CHIRALCEL D-3 column, 4.6 mm 250 mm, Daicel Chemical Industries, hexane/2-propanol = 97:3, 0.5 ml/min, 40 C, 254 nm UV detector, retention time = 19.5 min for R isomer and 20.9 min for S isomer] revealed that the enantiomeric excess of 4aa was 77%. The absolute configuration of 4aa was assigned by consideration of the stereochemical pathway. (R)-2-(5-Vinylnonyl)-1,3-dioxane (4bb) 2 The product 4bb was purified by flash chromatography on silica gel (0 5% EtAc/hexane) (93% isolated yield). Colorless il. IR (neat) 908, 995, 1144, 1640, 2851, 2925 cm 1. 1 H NMR (300 MHz, CDCl 3 ) 0.87 (t, J = 7.2 Hz, 3H), (m, 13H), (m, 2H), (m, 1H), (m, 1H), 3.76 (td, J = 12.0, 2.1 Hz, 2H), 4.10 (dd, J = 10.5, 4.8 Hz, 2H), 4.50 (t, J = 5.1 Hz, 1H), (m, 2H), 5.51 (ddd, J = 16.8, 10.5, 8.7 Hz, 1H). 13 C NMR (75.4 MHz, CDCl 3 ) 13.98, 22.70, 23.95, 25.74, 26.87, 29.29, 34.63, 34.75, 35.12, 43.86, 66.87, , , HRMS EI (m/z): [M H] + calcd for C 15 H 27 2, ; found, [ ] 25 D (c 1.20, CHCl 3 ). The ee value (88% ee) was determined by chiral HPLC analysis of the p-nitrobenzoate derivative obtained by the ozonolysis, reduction with NaBH 4 followed by benzoylation from 4bb S5

6 [CHIRALCEL D-3 column, 4.6 mm 250 mm, Daicel Chemical Industries, hexane/2-propanol = 99:1, 0.5 ml/min, 40 C, 254 nm UV detector, retention time = 42.3 min for R isomer and 44.2 min for S isomer]. The literature data of the p-nitrobenzoate derivative confirmed the (R) absolute configuration of 4bb ) 3, MeH/Et 2, 78 C 2) NaBH 4, 78 C to rt 2 H p-nitrobenzoylchloride DMAP, CH 2 Cl 2 rt, 2 h N 2 2 for HPLC and absolute configuration (S)-2-(10-Chloro-6-vinyldecyl)-1,3-dioxane (4cc) Cl 2 3 The product 4cc was purified by flash chromatography on silica gel (0 5% EtAc/hexane) followed by GPC (CHCl 3 ) (71% isolated yield). Colorless il. IR (neat) 910, 995, 1144, 1640, 2851, 2925 cm 1. 1 H NMR (300 MHz, CDCl 3 ) (m, 13H), (m, 2H), (m, 2H), (m, 1H), (m, 1H), 3.52 (t, J = 6.6 Hz, 2H), 3.76 (td, J = 12.3, 2.4 Hz, 2H), (m, 2H), 4.50 (t, J = 5.2 Hz, 1H), 4.93 (dd, J = 16.5, 2.1 Hz, 1H), 4.96 (dd, J = 10.2, 2.1 Hz, 1H), 5.49 (ddd, J = 16.5, 10.2, 8.7 Hz, 1H). 13 C NMR (75.4 MHz, CDCl 3 ) 23.81, 24.41, 25.74, 26.87, 29.42, 32.63, 34.09, 34.76, 35.12, 43.89, 45.03, 66.87, , , HRMS EI (m/z): [M H] + calcd for C 16 H 28 Cl 2, ; found, [ ] 25 D (c 1.10, CHCl 3 ). The ee value (83% ee) was determined by chiral HPLC analysis of the p-nitrobenzoate derivative obtained by the ozonolysis, reduction with NaBH 4 followed by benzoylation from 4cc [CHIRALCEL D-3 column, 4.6 mm 250 mm, Daicel Chemical Industries, hexane/2-propanol = 97:3, 0.5 ml/min, 40 C, 254 nm UV detector, retention time = 35.4 min for R isomer and 39.1 min for S isomer]. The absolute configuration of 4cc was assigned by consideration of the stereochemical pathway. (S)-Triisopropyl[(6-phenethyl-7-octen-1-yl)oxy]silane (4da) Ph TIPS 3 The product 4da was purified by flash chromatography on silica gel (0 5% EtAc/hexane) (71% isolated yield). Colorless il. IR (neat) 679, 882, 1103, 1462, 2864, 2931 cm 1. 1 H NMR (300 MHz, CDCl 3 ) (m, 21H), (m, 6H), (m, 3H), (m, 1H), (m, 1H), 2.51 (ddd, J = 13.8, 10.2, 6.6 Hz, 1H), 2.65 (ddd, J = 13.8, 10.2, 5.2 Hz, 1H), 3.65 (t, J = 6.6 Hz, 2H), (m, 2H), 5.57 (ddd, J = 17.1, 10.4, 8.7 Hz, 1H), (m, 3H), (m, 2H). 13 C NMR (75.4 MHz, CDCl 3 ) , 18.33, 26.23, 27.25, 33.32, 33.87, 35.37, 37.18, 44.11, 63.84, , , , , , HRMS EI (m/z): [M-C 3 H 7 ] + calcd for C 22 H 37 Si, ; found, [ ] 25 D 3.07 (c 1.01, CHCl 3 ). S6

7 The ee value (88% ee) was determined by chiral HPLC analysis of the alcohol derivative obtained by hydoroboration from 4da [CHIRALCEL D-3 column, 4.6 mm 250 mm, Daicel Chemical Industries, hexane/2-propanol = 98:2, 0.5 ml/min, 40 C, 254 nm UV detector, retention time = 27.2 min for R isomer and 31.4 min for S isomer]. The absolute configuration of 4da was assigned by consideration of the stereochemical pathway. TIPS Ph 3 9-BBN-H (1.2 eq) 60 C, 1 h then H 2 2 aq 2M NaH aq TIPS Ph 3 H for HPLC (R)-Triisopropyl[(6-methyl-7-octen-1-yl)oxy]silane (4dd) TIPS 3 The product 4dd was purified by flash chromatography on silica gel (hexane) (62% isolated yield). Colorless il. IR (neat) 881, 909, 994, 1103, 1462, 2865, 2930 cm 1. 1 H NMR (300 MHz, CDCl 3 ) 0.97 (d, J = 6.9 Hz, 3H), (m, 21H), (m, 6H), (m. 2H), 2.10 (m, 1H), 3.66 (t, J = 12.3 Hz, 3H), (m, 2H), 5.69 (ddd, J = , 7.8 Hz, 1H). 13 C NMR (75.4 MHz, CDCl 3 ) 11.88, 17.91, 20.06, 25.82, 26.97, 32.92, 36.56, 37.65, 63.43, , HRMS EI (m/z): [M C 3 H 7 ] + 22 calcd for C 15 H 31 Si, ; found, [ ] D 4.36 (c 1.08, CHCl 3 ). The ee value (72% ee) was determined by chiral HPLC analysis of the p-nitrobenzoate derivative obtained by the ozonolysis, reduction with NaBH 4 benzoylation followed by desilylation from 4dd [CHIRALCEL J-3 column, 4.6 mm 250 mm, Daicel Chemical Industries, hexane/2-propanol = 95:5, 0.5 ml/min, 40 C, 254 nm UV detector, retention time = 40.3 min for R isomer and 42.4 min for S isomer].the absolute configuration of 4dd was a assigned by consideration of the stereochemical pathway. 1) 3, MeH/Et 2, 78 C TIPS TIPS H 3 2) NaBH 4, 78 C to rt 3 1) p-nitrobenzoylchloride DMAP, CH 2 Cl 2, rt, 2 h 2) TBAF, THF, rt, 1 h H 3 for HPLC N 2 (R)-[(6-Cyclohexyl-7-octen-1-yl)oxy]triisopropylsilane (4de) TIPS 3 The product 4de was purified by flash chromatography on silica gel (hexane) followed by GPC (CHCl 3 ) (53% isolated yield). Colorless il. IR (neat) 679, 882, 909, 997, 1103, 1449, 1639, 2864, 2924 cm 1. 1 H NMR (300 MHz, CDCl 3 ) (m, 32H), 1.06 (s, 9H), 3.66 (t, J = 12.3 Hz, 2H), 4.89 (dd, J = 17.1, 2.1 Hz, 1H), 4.97 (dd, J = 9.9, 2.1 Hz, 1H), 5.54 (dt, J = 17.1, 9.1 Hz, 1H). 13 C NMR (75.4 MHz, CDCl 3 ) 11.88, 17.92, 25.83, 26.59, 26.62, 26.66, 27.25, 29.55, 31.07, 31.56, S7

8 32.93, 41.69, 50.02, 63.46, , HRMS EI (m/z): [M C 3 H 7 ] + calcd for C 20 H 39 Si, ; found, [ ] 25 D 4.08 (c 1.12, CHCl 3 ). The ee value (76% ee) was determined by chiral HPLC analysis of the p-nitrobenzoate derivative obtained by the ozonolysis, reduction with NaBH 4 followed by benzoylation from 4de [CHIRALCEL D-3 column, 4.6 mm 250 mm, Daicel Chemical Industries, hexane, 0.25 ml/min, 40 C, 254 nm UV detector, retention time = 61.0 min for R isomer and 67.2 min for S isomer].the absolute configuration of 4de was a assigned by consideration of the stereochemical pathway. (S)-6-Phenethyl-7-octen-1-yl Pivalate (4ea) Ph Piv 3 The product 4ea was purified by flash chromatography on silica gel (0 5% EtAc/hexane) (73% isolated yield). Colorless il. IR (neat) 698, 910, 1151, 1284, 1455, 1480, 1727, 2931 cm 1. 1 H NMR (300 MHz, CDCl 3 ) 1.19 (s, 9H), (m, 6H), (m, 4H), (m, 1H), 2.51 (ddd, J = 13.8, 10.2, 6.6 Hz, 1H), 2.65 (ddd, J = 13.8, 10.2, 5.4 Hz, 1H), 4.03 (t, J = 6.6 Hz, 2 H), (m, 2H), 5.57 (ddd, J = 17.1, 10.2, 8.7 Hz, 1H), , (m, 3H), (m, 2H). 13 C NMR (75.4 MHz, CDCl 3 ) 25.92, 26.65, 27.09, 28.43, 33.43, 34.84, 36.77, 38.63, 43.66, 64.38, , , , , , , HRMS EI (m/z): [M] + calcd for C 21 H 32 2, ; found, [ ] 25 D 4.30 (c 1.25, CHCl 3 ). The ee value (88% ee) was determined by chiral HPLC analysis of the p-nitrobenzoate derivative obtained by the ozonolysis, reduction with NaBH 4 followed by benzoylation from 4ea [CHIRALCEL D-3 column, 4.6 mm 250 mm, Daicel Chemical Industries, hexane/2-propanol = 95:5, 0.5 ml/min, 40 C, 254 nm UV detector, retention time = 20.5 min for S isomer and 22.5 min for R isomer]. The absolute configuration of 4ea was assigned by consideration of the stereochemical pathway. (S)-2-{10-[(tert-Butyldimethylsilyl)oxy]-6-vinyldecyl}isoindoline-1,3-dione (4ff) TBS 3 N 3 The product 4ff was purified by flash chromatography on silica gel (0 5% EtAc/hexane) followed by GPC (CHCl 3 ) (73% isolated yield). Colorless il. IR (neat) 718, 774, 834, 1096, 1254, 1395, 1712, 2857, 2929 cm 1. 1 H NMR (300 MHz, CDCl 3 ) 0.04 (s, 6H), 0.89 (s, 9H), (m, 10H), (m, 2H), (m, 2H), (m, 1H), 3.58 (t, J = 6.6 Hz, 2H), 3.67 (t, J = 7.5 Hz, 2H), 4.91 (dd, J = 16.8, 2.1 Hz, 1H), 4.94 (dd, J = 10.5, 2.1 Hz, 1H), 5.48 (ddd, J = 16.8, 10.5, 8.7 Hz, 1H), (m, 2H), (m, 2H). 13 C NMR (75.4 MHz, CDCl 3 ) 5.42, 18.24, 23.22, 25.87, 26.63, 26.87, 28.46, 32.83, 34.66, 34.71, 37.99, 43.96, 63.22, , , , , , HRMS ESI (m/z): [M+Na] + calcd for C 26 H 41 3 NNaSi, ; found, [ ] 25 D 0.41 (c 1.05, CHCl 3 ). S8

9 The ee value (88% ee) was determined by chiral HPLC analysis of the p-nitrobenzoate derivative obtained by the ozonolysis, reduction with NaBH 4 followed by benzoylation from 4ff [CHIRALCEL AD-H column, 4.6 mm 250 mm, Daicel Chemical Industries, hexane/2-propanol = 97:3, 0.5 ml/min, 40 C, 254 nm UV detector, retention time = 32.2 min for R isomer and 35.1 min for S isomer]. The absolute configuration of 4ff was assigned by consideration of the stereochemical pathway. (S)-2-(10-Chloro-6-vinyldecyl)isoindoline-1,3-dione (4fc) Cl N 3 The product 4fc was purified by flash chromatography on silica gel (0 5% EtAc/hexane) (72% isolated yield). Colorless il. IR (neat) 717, 911, 1394, 1708, 1773, 2932 cm 1. 1 H NMR (300 MHz, CDCl 3 ) (m, 10H), (m, 4H), (m, 1H), 3.52 (t, J = 6.6 Hz, 2H), 3.67 (t, J = 7.2 Hz, 2H), 4.93 (dd, J = 16.8, 1.8 Hz, 1H), 4.95 (dd, J = 10.2, 1.8 Hz, 1H) 5.48 (ddd, J = 16.8, 10.2, 9.0 Hz, 1H), (m, 2H), (m, 2H). 13 C NMR (75.4 MHz, CDCl 3 ) 24.38, 26.57, 26.80, 28.41, 32.61, 34.09, 34.68, 37.94, 43.83, 45.03, , , , , , HRMS ESI (m/z): [M+Na] + calcd for C 20 H 26 2 NClNa, ; found, [ ] 25 D (c 1.07, CHCl 3 ). The ee value (90% ee) was determined by chiral HPLC analysis of the p-nitrobenzoate derivative obtained by the ozonolysis, reduction with NaBH 4 followed by benzoylation from 4fc [CHIRALCEL AD-H column, 4.6 mm 250 mm, Daicel Chemical Industries, hexane/2-propanol = 97:3, 0.5 ml/min, 40 C, 254 nm UV detector, retention time = min for R isomer and min for S isomer]. The absolute configuration of 4fc was assigned by consideration of the stereochemical pathway. (R)-Dimethylphenyl(1-undecen-3-yl)silane (4hg) PhMe 2 Si 5 The product 4hg was purified by flash chromatography on silica gel (hexane) (77% isolated yield). Colorless il. IR (neat) 698, 811, 1113, 1248, 1428, 1626, 2924 cm 1. 1 H NMR (300 MHz, CDCl 3 ) 0.25 (s, 3H), 0.26 (s, 3H), 0.86 (t, J = 6.6 Hz, 3H), (m, 14H), (m, 1H), (m, 1H), 4.88 (dd, J = 10.2, 2.1 Hz, 1H), 5.58 (dt, J = 17.1, 10.2 Hz, 1H), (m, 3H), (m, 2H). 13 C NMR (75.4 MHz, CDCl 3 ) 5.78, 5.02, 13.58, 22.15, 27.89, 28.74, 28.81, 28.87, 28.99, 31.37, 33.87, , , , , , HRMS EI (m/z): [M] + calcd for C 19 H 32 Si, ; found, [ ] 27 D 7.05 (c 1.23, CHCl 3 ). HPLC analysis [CHIRALCEL J-3 column, 4.6 mm 250 mm/j-3 column, 4.6 mm 250 mm/j-h column, 4.6 mm 250 mm, Daicel Chemical Industries, hexane, 0.25 ml/min, 40 C, 254 nm UV detector, retention time = 55.0 min for S isomer and 56.4 min for R isomer] revealed S9

10 that the enantiomeric excess of 4hg was 91%. The absolute configuration of 4hg was determined by transforming it to the chiral secondary alcohol by alkene reduction followed by Fleming Tamao oxidation 3 with retention of configuration. [ ] 25 D (c 0.51, CHCl 3 ). {lit 4, (S) isomer, 84% ee, [ ] 20 D +5.2 (c 1, CHCl 3 ).} PhMe 2 Si 5 (R) TsNHNH 2 (10 eq) Et 3 N (10 eq) dioxane 120 C, 1 h PhMe 2 Si 5 HBF 4 Et 2 (2.8 eq) CH 2 Cl 2, rt, 1 h FMe 2 Si 5 H 2 2 (10 eq) KHC 3 (10 eq) KF (4 eq) H 59% in 3 steps MeH/THF 5 (S) 40 C, 6 h for absolute configuration (R)-[8-(1,3-Dioxan-2-yl)-1-octen-3-yl]dimethylphenylsilane (4cg) PhMe 2 Si 3 The product 4cg was purified by flash chromatography on silica gel (0 5% EtAc/hexane) followed by GPC (CHCl 3 ) (66% isolated yield). Colorless il. IR (neat) 699, 996, 1144, 1246, 1625, 2850, 2953 cm 1. 1 H NMR (300 MHz, CDCl 3 ) 0.25 (s, 3H), 0.26 (s, 3H), (m, 9H), (m, 2H), (m, 1H), (m, 1H), 3.74 (dt, J = 12.0, 2.4 Hz, 2H), (m, 2H), 4.47 (t, J = 5.1 Hz, 1H), (m, 1H), 4.87 (dd, J = 10.2, 1.8 Hz, 1H), 5.56 (dt, J = 17.1, 10.2 Hz, 1H), (m, 3H), (m, 2H). 13 C NMR (75.4 MHz, CDCl 3 ) 5.36, 4.64, 23.78, 25.73, 28.20, 29.02, 29.10, 34.26, 35.11, 66.85, , , , , , , HRMS ESI (m/z): [M+Na] + calcd for C 20 H 32 2 NaSi, ; found, [ ] 26 D 5.64 (c 1.17, CHCl 3 ). HPLC analysis [CHIRALCEL D-3 column, 4.6 mm 250 mm, Daicel Chemical Industries, hexane/2-propanol = 99.9:0.1, 0.5 ml/min, 40 C, 254 nm UV detector, retention time = 17.4 min for S isomer and 18.1 min for R isomer] revealed that the enantiomeric excess of 4cg was 91%. The absolute configuration of 4cg was assigned by consideration of the stereochemical pathway. (R)-2-[6-(Dimethylphenylsilyl)-7-octen-1-yl]isoindoline-1,3-dione (4fg) PhMe 2 Si N 3 The product 4fg was purified by flash chromatography on silica gel (0 5% EtAc/hexane) (85% isolated yield). Colorless il. IR (neat) 717, 1394, 1624, 1708, 1773, 2931 cm 1. 1 H NMR (300 MHz, CDCl 3 ) 0.24 (s, 3H), 0.25 (s, 3H), (m, 6H), (m, 3H), 3.63 (t, J = 7.2 Hz, 2H), (m, 1H), 4.86 (dd, J = 10.2, 1.8 Hz, 1H), 5.55 (dt, J = 17.1, 10.2 Hz, 1H), (m, 3H), (m, 2H), (m, 2H), (m, 2H). 13 C NMR (75.4 MHz, CDCl 3 ) 5.44, 4.64, 26.52, 28.13, 28.39, 28.76, 34.22, 37.98, , , , , , , , , , HRMS ESI (m/z): [M+Na] + calcd for C 24 H 29 2 NNaSi, ; found, [ ] 27 D (c 0.75, CHCl 3 ). S10

11 HPLC analysis [CHIRALCEL D-3 column, 4.6 mm 250 mm, Daicel Chemical Industries, hexane/2-propanol = 99.5:0.5, 0.5 ml/min, 40 C, 254 nm UV detector, retention time = 31.6 min for S isomer and 33.4 min for R isomer] revealed that the enantiomeric excess of 4fg was 90%. The absolute configuration of 4fg was assigned by consideration of the stereochemical pathway. (R)-(9-Chloro-1-nonen-3-yl)dimethylphenylsilane (4ig) Cl PhMe 2 Si 4 The product 4ig was purified by flash chromatography on silica gel (hexane) (88% isolated yield). Colorless il. IR (neat) 699, 894, 1122, 1248, 1427, 1625, 2855, 2928 cm 1. 1 H NMR (300 MHz, CDCl 3 ) 0.25 (s, 3H), 0.26 (s, 3H), (m, 8H), (m, 3H), 3.49 (t, J = 6.9 Hz, 2H), (m, 1H), 4.89 (dd, J = 9.9, 1.8 Hz, 1H), 5.58 (dt, J = 17.1, 9.9 Hz, 1H), (m, 3H), (m, 2H). 13 C NMR (75.4 MHz, CDCl 3 ) 5.44, 4.61, 26.62, 28.15, 28.42, 28.89, 32.48, 34.23, 45.08, , , , , , HRMS FI (m/z): [M] + calcd for C 17 H 27 ClSi, ; found, [ ] 25 D (c 1.30, CHCl 3 ). HPLC analysis [CHIRALCEL J-3 column, 4.6 mm 250 mm/j-h column, 4.6 mm 250 mm, Daicel Chemical Industries, hexane, 0.25 ml/min, 40 C, 254 nm UV detector, retention time = 36.9 min for S isomer and 38.1 min for R isomer] revealed that the enantiomeric excess of 4ig was 91%. The absolute configuration of 4ig was assigned by consideration of the stereochemical pathway. (R)-6-(Dimethylphenylsilyl)-7-octen-1-yl Pivalate (4eg) Piv PhMe 2 Si 3 The product 4eg was purified by flash chromatography on silica gel (0 5% EtAc/hexane) (52% isolated yield). Colorless il. IR (neat) 600, 812, 1152, 1284, 1626, 1727, 2932 cm 1. 1 H NMR (300 MHz, CDCl 3 ) 0.25 (s, 3H), 0.26 (s, 3H), 1.18 (s, 9H), (m, 6H), (m, 2H), (m, 1H), 4.00 (t, J = 6.6 Hz, 2H), (m, 1H), 4.88 (dd, J = 10.2, 1.8 Hz, 1H), 5.57 (dt, J = 17.1, 10.2 Hz, 1H), (m, 3H), (m, 2H). 13 C NMR (75.4 MHz, CDCl 3 ) 5.44, 4.62, 25.52, 27.09, 28.17, 28.41, 28.73, 34.22, 38.61, 64.39, , , , , , , HRMS ESI (m/z): [M+Na] + calcd for C 21 H 34 2 NaSi, ; found, [ ] 25 D 8.09 (c 1.27, CHCl 3 ). HPLC analysis [CHIRALCEL D-3 column, 4.6 mm 250 mm, Daicel Chemical Industries, hexane, 0.25 ml/min, 40 C, 254 nm UV detector, retention time = 41.1 min for S isomer and 43.0 min for R isomer] revealed that the enantiomeric excess of 4eg was 87%. The absolute configuration of 4eg was assigned by consideration of the stereochemical pathway. S11

12 Ligand Effects Figure S1 Ph Me Me Cl 3a (0.2 mmol) + 2a (0.25 mmol) B CuCl (5 mol %) ligand (5 mol %) MeK (0.21 mmol) 1,4-dioxane 35 C, 12 h Me Me Ph (S) 4aa : > 20:1 t Bu Me t Bu Me t Bu Me Me Me P P t Bu t Bu 2 Me Me P P t Bu t Bu 2 P P t Bu t Bu 2 P P Me Me 2 t Bu (R)-DTBM-BINAP 5%, 37% ee Me 2 t Bu Me (R)-DTBM-Me-BIPHEP 25%, 47% ee 2 Me t Bu 2 (R)-DTBM-SEGPHS 48%, 61% ee Me Me 2 (R)-DMM-SEGPHS no reaction Me t Bu PPh 2 PPh 2 PPh 2 PPh 2 N N P P N N (R)-SEGPHS no reaction (R)-BINAP no reaction t Bu Me (R,R)-QuinoxP* 99%, 7% ee PF 6 3%, racemic References (1) Magid, R. M.; Fruchey,. S.; Johnson, W. L. Tetrahedron Lett. 1977, 18, (2) Nagao, K.; Yokobori, U.; Makida, Y.; hmiya, H.; Sawamura, M. J. Am. Chem. Soc. 2012, 134, (3) (a) Fleming, I.; Henning, R.; Plaut, H. J. Chem. Soc., Chem. Commun. 1984, (b) Jones, G. R.; Landais, Y. Tetrahedron 1996, 52, (4) Västilä, P.; Pastor, I. M. B.; Andolfsson, H. J. rg. Chem. 2005, 70, S12

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