Supplementary Material

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1 Supplementary Material Chiral N-aryl tert-butanesulfinamide-olefin ligands for rhodium-catalyzed asymmetric 1,4-addition Shuai Yuan, Qingle Zeng,* Jiajun Wang, Lihong Zhou State Key Laboratory of Geohazard Prevention and Geoenvironment Protection (Chengdu University of Technology), College of Materials, Chemistry & Chemical Engineering, Chengdu University of Technology, 1#, Dongsanlu, Erxianqiao, Chengdu , Sichuan, P. R. China Table of Contents 1. General S2 2. Procedure of synthesis of chiral ligands L1 to L4 S2 3. Procedure of rhodium-catalyzed 1,4-addition reaction S2 4. Spectral data of Chiral Ligands S3 5. Spectral data and chiral HPLC traces of measured reaction products S5 6. References S17 7. NMR Spectra collection S18 Page S1

2 General All reactions were carried out under an argon atmosphere. All glassware used was dried in electric oven at 120 o C. All chemicals were purchased from Aldrich, Alfa Aesar, Adamas, Aladdin, and Chengdu Changzheng Chemical Company and used as received. Petroleumether (PE) refers to the fraction boiling in the C range. All compounds were characterized by 1 H NMR, 13 C NMR, HR-MS and IR spectroscopy, unless otherwise mentioned. Nuclear magnetic resonance spectra were recorded on a 300MHz instrument or 400 MHz instrument. All 1 H NMR experiments are reported in δ units, parts per million (ppm), and were measured relative to the signals for residual chloroform (7.26 ppm), DMSO (2.50 ppm) or acetone (2.05 ppm) in the deuterated solvent, unless otherwise stated. All 13 C NMR spectra are reported in ppm relative to deuterochloroform (77.2 ppm), DMSO-d 6 (39.5 ppm) or acetone-d 6 (206.7 ppm for C=O) unless otherwise stated, and all were obtained with 1 H decoupling. All IR spectra were taken on an infrared spectrometer. High-resolution mass spectra are recorded on an LCMS-IT-TOF instrument. Chiral HPLC analyses were performed on a Shimadzu liquid chromatography with a Chiralcel OD-H, AD-H, AS-H chiral column (4.6 mm 250 mm 5 μm). All rotation data are recorded on an auto rotation (Na D line, cell long 10 cm, λ = 589 nm). Procedure of synthesis of chiral ligands L1 to L4 An oven-dried round-bottom flask with a magnetic stir bar and fitted with a rubber septum, was charged with (R)-tert-butanesulfinamide (13.0 mmol), Pd 2 (dba) 3 (0.26 mmol), tbu-xphos (0.45 mmol), NaOH (26 mmol), bromobenzene (10.0 mmol), toluene (20 ml), and degassed water (3.0 ml).the vessel was evacuated and backfilled with argon for three times. The solution was stirred at 90 o C for 20 h. when cooled to room temperature, quenched by water, and extracted with ethyl acetate (35 ml) for three times. The combined organic layer was dried over anhydrous MgSO 4. The filtrate was condensed under vacuum. The resulting residual was purified with silica gel column chromatography with a solution of petroleum ether and ethyl acetate (5:1 (v:v)) as an eluent to afford N-aryl tert-butanesulfinamide. To an oven-dry round-bottom flask with a magnetic stir bar was added N-phenyl (R)-tert-butanesulfinamide (4.0 mmol), 60% NaH (8 mmol), and THF (15 ml). The vessel was evacuated and backfilled with argon for three times. Then the mixture was stirred in an ice water bath for 1 h, and then added cinnamyl bromide (1.2 mmol) by syringe to the flask. The reaction mixture was stirred overnight. Then quenched by saturated NH 4 Cl solution, the reaction mixture was extracted with ethyl acetate (20 ml) three times. The combined organic layer was washed with saturated NaCl solution and then dried over anhydrous MgSO 4. The filtrate was condensed under vacuum. The residual was purified with a silica gel column chromatography with a mixed solution of petroleum ether and ethyl acetate (5:1(v:v)) as an eluent to afford (R)-N-cinnamyl-2-methyl-N-phenylpropane-2-sulfinamide (L2). Chiral ligands L1, L3, L4 adopted the same synthetic methods as L2. Procedure of rhodium-catalyzed 1,4-addition reaction To an oven-dry test tube with a ground joint neck with a magnetic stir bar were added enone (1.00 mmol), arylboronic acid (1.5 mmol), [RhCl(C 2 H 4 ) 2 ] 2 (0.015 mmol), Ligand (0.035 mmol) in 1,4-dioxane (3.0 ml). The vessel was evacuated and backfilled with argon for three times. The solution was stirred at 40 o C for 30 min, and then aqueous K 3 PO 4 (0.5 mmol) was added by syringe to the flask. After being stirred at 40 o C for 3 h, the reaction mixture was then cooled to room temperature, quenched by water, and extracted with ethyl acetate (15 ml) for three times. The combined organic layer was dried over anhydrous MgSO 4. The filtrate was condensed in vacuum. The residual was purified with silica gel column chromatography with a solution of petroleum ether and ethyl acetate as an eluent to afford the product. The ee was determined by chiral HPLC. Page S2

3 14.758' ' General Papers Spectral data of Chiral Ligands (R)-N-cinnamyl-2-methyl-N-phenylpropane-2-sulfinamide (L2) White solid. Yield: 25.3 mg (81%). Mp o C. [ ] 20.5 D +105 (c 0.21, CH 2 Cl 2 ). 1 H NMR (400 MHz, DMSO-d 6 ) δ (m, 2H), (m, 4H), 7.07 (dd, J = 16.2, 8.0 Hz, 2H), 6.58 (dt, J = 14.4, 7.6 Hz, 4H), 6.36 (dt, J = 16.0, 5.6 Hz, 1H), (m, 2H), 1.05 (s, 7H). 13 C NMR (101 MHz, DMSO-d 6 ) δ (s), (s), (s), (s), (s), (s), (s), (d, J = 6.9 Hz), (s), (s), (s), (s), (s). IR (KBr), ν (cm -1 ): 3056, 3025, 2936, 1655, 1592, 1472, 1363, 1298, 1246, 1176, 1075, 968, 852, 781. ESI-MS (positive mode), m/z = 336 [M + Na] +. HR-MS (ESI-TOF) m/z calcd for C 19 H 23 NNaOS [M+Na + ] ; found HPLC: Chiralcel OD-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 95:5; flow rate: 0.7 ml/min; retention time: 12.7 min (minor), 15.2 min (major). Measured ee value = 97 %. mv min Height Total Height Total (R)-N-([1,1'-biphenyl]-4-yl)-N-allyl-2-methylpropane-2-sulfinamide (L3) White solid. Yield: 21.0 mg (80%). Mp o C. [ ] 21.0 D (c 0.12, CH 2 Cl 2 ). 1 H NMR (400 MHz, CDCl 3 ) δ (m, 4H), (m, 2H), 7.32 (ddt, J = 9.5, 8.2, 4.1 Hz, 1H), (m, 2H), (m, 1H), (m, 2H), (m, 1H), (m, 1H), 1.26 (d, J = 11.7 Hz, 9H). 13 C NMR (101 MHz, DMSO-d 6 ) δ (s), Page S3

4 (s), (s), (d, J = 18.4 Hz), (s), (s), (s), (s), (s), (s), (s), (s), (s). IR (KBr), ν (cm -1 ): 3050, 2959, 1601, 1519, 1484, 1450, 1364, 1295, 1251, 1204, 1142, 1091, 1055, 995, 918, 827, 757, 692. ESI-MS (positive mode), m/z = 336 [M + Na] +. HR-MS (ESI-TOF) m/z calcd for C 19 H 23 NOS [M+Na + ] ; found HPLC: Chiralcel OD-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 95:5; flow rate: 0.7 ml/min; retention time: 5.5 min (minor), 10.6 min (major). (R)-N-([1,1'-biphenyl]-4-yl)-N-cinnamyl-2-methylpropane-2-sulfinamide (L4) Yellow solid. Yield: 23.3mg (81%). Mp o C. [ ] 21.2 D (c 0.14, CH 2 Cl 2 ). 1 H NMR (400 MHz, CDCl 3 ) δ (m, 4H), (m, 2H), 7.30 (ddd, J = 8.8, 7.4, 2.0 Hz, 6H), 7.21 (ddd, J = 6.8, 3.8, 1.6 Hz, 1H), 6.51 (d, J = 16.0 Hz, 1H), 6.19 (dt, J = 16.0, 5.9 Hz, 1H), 4.45 (ddd, J = 16.8, 6.2, 1.5 Hz, 1H), 4.24 (ddd, J = 16.8, 5.6, 1.5 Hz, 1H), 1.28 (d, J = 11.9 Hz, 8H). 13 C NMR (101 MHz, DMSO-d 6 ) δ (s), (s), (s), (s), (s), (s), (s), (s), (s), (t, J = 13.6 Hz), (d, J = 5.3 Hz), (s), (s), (s), (s), (s), (s). IR (KBr), ν (cm -1 ): 3041, 2938, 1602, 1519, 1486, 1364, 1305, 1254, 1203, 1083, 1050, 962, 845, 733, 694. ESI-MS (positive mode), m/z = 412 ([M + Li] + ). HR-MS (ESI-TOF) m/z calcd for C 25 H 27 NNaOS [M+Na + ] ; found HPLC: Chiralcel OD-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 95:5; flow rate: 0.7 ml/min; retention time: 15.3 min (minor), 20.3 min (major). Page S4

5 Spectral data and chiral HPLC traces of measured reaction products (S)-3-(p-Tolyl)cyclohexanone [1] 3a: 1 H NMR (400 MHz, CDCl 3 ) δ (m, 4H), 3.11 (tt, J = 11.6, 4.0 Hz, 1H), (m, 1H), (m, 3H), 2.46 (d, J = 8.5 Hz, 3H), (m, 2H), (m, 2H). 13 C NMR (101 MHz, CDCl 3 ) δ (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s). HPLC: Chiralpak AD-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 95:5; flow rate: 0.7 ml/min; retention time: 7.6 min (major), 8.4 min (minor). Measured ee value = 89 % Total Total O 3-phenylcyclohexanone [4] 3b: 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), 3.00 (tt, J = 11.7, 4.0 Hz, 1H), (m, 4H), (m, 2H), (m, 2H). 13 C NMR (101 MHz, CDCl 3 ) δ (s), (s), (s), (s), (s), (s), (s), (s), (s), (s). HPLC: Chiralpak AD-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 90:10; flow rate: 0.7 ml/min; retention time: 10.5 min (minor), 11.7 min (major). Measured ee value = 83 %. Page S5

6 Total Total O 3-(3-methylphenyl)cyclohexanone [2] 3c: 1 H NMR (400 MHz, CDCl 3 ) δ 7.23 (dd, J = 14.7, 7.1 Hz, 1H), 7.04 (t, J = 10.2 Hz, 3H), (m, 1H), (m, 1H), (m, 6H), (m, 3H), (m, 2H). 13 C NMR (101 MHz, CDCl 3 ) δ (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s). HPLC: Chiralcel OD-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 90:10; flow rate: 0.7 ml/min; retention time: 8.8 min (major), 10.2 min (minor). Measured ee value = 75 % Total Total O 3-(o-Tolyl)cyclohexanone [1] Page S6

7 3d: 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), 7.12 (qd, J = 7.8, 3.3 Hz, 2H), (m, 1H), (m, 4H), 2.30 (s, 3H), (m, 1H), (m, 1H), (m, 2H). 13 C NMR (101 MHz, CDCl 3 ) δ (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s). HPLC: Chiralpak AD-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 90:10; flow rate: 0.7 ml/min; retention time: 6.7 min (minor), 7.9 min (major). Measured ee value = 81 % Total Total (S)-3-(4-(tert-Butyl)phenyl)cyclohexanone [4] 3e: [ ] 32.5 D (c 0.16, CHCl 3 ). [lit. [9]: [ ] 20 D = (c 0.63, CHCl 3 ), For R-isomer]. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), 3.00 (tt, J = 11.7, 3.9 Hz, 1H), (m, 4H), (m, 2H), (m, 2H), 1.32 (s, 9H). 13 C NMR (101 MHz, DMSO-d 6 ) δ (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s). HPLC: Chiralpak AS-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 90:10; flow rate: 0.7 ml/min; retention time: 8.4 min (major), 10.7 min (minor). Measured ee value = 93%. Page S7

8 Total Total O 3-(4-vinylphenyl)cyclohexan-1-one 3f: 1 H NMR (400 MHz, CDCl 3 ) δ 7.38 (d, J = 8.2 Hz, 2H), 7.18 (d, J = 8.2 Hz, 2H), 6.70 (dd, J = 17.6, 10.9 Hz, 1H), 5.73 (dd, J = 17.6, 0.8 Hz, 1H), (m, 1H), 3.00 (tt, J = 11.6, 4.0 Hz, 1H), (m, 4H), (m, 1H), 2.05 (ddd, J = 20.0, 11.7, 4.0 Hz, 1H), (m, 2H). 13 C NMR (101 MHz, CDCl 3 ) δ (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s). HPLC: Chiralpak AS-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 90:10; flow rate: 0.7 ml/min; retention time: 13.3 min, 17.0 min (major). Measured ee value = 85% Total Total (S)-3-(naphthalen-2-yl)cyclohexan-1-one [4] 3g: [ ] 32.3 D (c 0.15, CHCl 3 ) [lit. [4]: [ ] 20 D -8.7 (c 0.072, CHCl 3 )]. 1 H NMR (400 MHz, CDCl 3 ) δ 7.81 (t, J = 7.4 Hz, 3H), 7.65 (s, 1H), (m, 2H), 7.37 (dd, J = 8.5, 1.8 Hz, 1H), 3.19 (tdd, J = 11.3, 5.3, 3.3 Hz, 1H), (m, 2H), (m, 2H), (m, 2H), (m, 2H). 13 C NMR (101 MHz, DMSO-d 6 ) δ (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s). HPLC: Chiralpak AS-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 90:10; flow rate: 0.7 ml/min; retention time: 15.3 min, 19.8 min (major). Measured ee value = 79%. Page S8

9 Total Total (S)-3-(4-Methoxyphenyl)cyclohexanone [1] 3h: 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), 3.79 (s, 3H), 2.96 (tt, J = 11.7, 3.9 Hz, 1H), (m, 4H), (m, 2H), (m, 2H). 13 C NMR (101 MHz, DMSO-d 6 ) δ (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s). HPLC: Chiralpak AD-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 90:10; flow rate: 0.7 ml/min; retention time: 9.5 min (major), 10.2 min (minor). Measured ee value = 85 % Total Total O Cl 3-(4-Chlorophenyl)cyclohexanone [8] 3i: 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), 2.92 (tt, J = 11.8, 3.9 Hz, 1H), (m, Page S9

10 4H), (m, 2H), (m, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ (s), (s), (s), (s), (s), (s), (s), (s), (s), (s). HPLC: Chiralpak AS-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 90:10; flow rate: 0.7 ml/min; retention time: 15.4 min (minor), 16.2 min (major). Measured ee value = 73% Total Total (S)-3-(3-Chlorophenyl)-cyclohexane [5] 3j: 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), 7.10 (t, J = 6.3 Hz, 1H), (m, 1H), 2.99 (tt, J = 11.9, 3.9 Hz, 1H), (m, 4H), (m, 2H), (m, 2H). 13 C NMR (101 MHz, CDCl 3 ) δ (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s). HPLC: Chiralpak AD-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 95:5; flow rate: 0.7 ml/min; retention time: 10.6 min (major), 11.9 min (minor). Measured ee value = 83% Total Total Page S10

11 (S)-3-(2-chlorophenyl)cyclohexan-1-one [9] 3k: [ ] D (c 0.31, CHCl 3 ) (lit. [9]: [ ] D = (c 0.51, CHCl 3 )). 1 H NMR (400 MHz, CDCl 3 ) δ (m, 1H), (m, 2H), 7.16 (tt, J = 6.3, 3.6 Hz, 1H), (m, 1H), 2.60 (ddt, J = 14.0, 4.1, 2.0 Hz, 1H), (m, 3H), (m, 2H), (m, 2H). 13 C NMR (101 MHz, CDCl 3 ) δ (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s). HPLC: Chiralpak AS-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 90:10; flow rate: 0.7 ml/min; retention time: 13.6 min, 16.6 min (major). Measured ee value = 83% Total Total O Br 3-(4-bromophenyl)cyclohexan [10] 3l: 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), 2.90 (tt, J = 11.8, 3.9 Hz, 1H), (m, 4H), (m, 2H), (m, 2H). 13 C NMR (101 MHz, CDCl3) δ (s), (s), (s), (s), (s), (s), (s), (s), (s), (s). HPLC: Chiralpak AS-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 90:10; flow rate: 0.7 ml/min; retention time: 16.6 min, 18.5 min (major). Measured ee value = 83%. Page S11

12 Total Total (S)-3-(4-Fluorophenyl)-cyclohexanone [1] 3m: 1 H NMR (400 MHz, CDCl 3 ) δ 7.18 (ddd, J = 7.0, 5.1, 2.5 Hz, 2H), 7.02 (ddd, J = 10.7, 5.9, 2.6 Hz, 2H), 3.00 (ddd, J = 15.7, 7.8, 3.9 Hz, 1H), (m, 4H), (m, 2H), (m, 2H). 13 C NMR (101 MHz, CDCl 3 ) δ (s), (s), (s), (d, J = 7.9 Hz), (d, J = 21.3 Hz), (s), (s), (s), (s), (s). HPLC: Chiralpak AD-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 95:5; flow rate: 0.7 ml/min; retention time: 10.9 min (major), 13.4 min (minor). Measured ee value = 55 % Total Total O 3-Phenylcyclopentanone [3] 3n: 1 H NMR (400 MHz, CDCl 3 ) δ 7.34 (ddd, J = 7.6, 5.9, 3.0 Hz, 2H), (m, 3H), (m, 1H), 2.67 (dd, J = 18.2, 7.4 Hz, 1H), (m, 4H), (m, 1H). 13 C NMR (101 MHz, DMSO-d 6 ) δ (s), (s), (s), (s), (s), (s), (s), (s), (s). HPLC: Chiralpak AS-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 98:2; flow rate: 1.0 ml/min; retention time: 21.4 min (major), 23.8 min (minor). Measured ee value = 93%. Page S12

13 Total Total O 3-(p-tolyl)cyclopentan-1-one [9] 3o: 1 H NMR (400 MHz, CDCl 3 ) δ 7.16 (s, 4H), 3.39 (tdd, J = 11.1, 7.4, 6.3 Hz, 1H), 2.66 (dd, J = 18.2, 7.5 Hz, 1H), (m, 2H), (m, 5H), (m, 1H). 13 C NMR (101 MHz, CDCl 3 ) δ (s), (s), (s), (s), (s), (s), (s), (s), (s), (s). HPLC: Chiralpak AS-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 95:5; flow rate: 0.7 ml/min; retention time: 15.2 min, 16.2 min (major). Measured ee value = 83% Total Total (S)-3-o-tolylcyclopentanone [6] Page S13

14 3p: 1 H NMR (400 MHz, CDCl 3 ) δ 7.21 (dt, J = 4.1, 1.9 Hz, 2H), (m, 2H), (m, 1H), 2.63 (dd, J = 18.1, 7.5 Hz, 1H), (m, 1H), 2.39 (d, J = 5.0 Hz, 3H), (m, 3H), (m, 1H). 13 C NMR (101 MHz, CDCl 3 ) δ (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s). HPLC: Chiralcel OD-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 90:10; flow rate: 0.7 ml/min; retention time: 11.5 min (major), 12.0 min (minor). Measured ee value = 95% Total Total O 3-(4-(tert-butyl)phenyl)cyclopentan-1-one [4] 3q: 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), 7.20 (d, J = 8.2 Hz, 2H), (m, 1H), 2.66 (dd, J = 18.2, 7.4 Hz, 1H), (m, 4H), (m, 1H), 1.32 (s, 9H). 13 C NMR (101 MHz, DMSO-d 6 ) δ (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s). HPLC: Chiralpak AS-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 90:10; flow rate: 0.7 ml/min; retention time: 7.3 min, 8.2 min (major). Measured ee value = 55% Page S14

15 Total Total (S)-3-(4-methoxyphenyl)cyclopentan-1-one [4] 3r: 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), 3.80 (s, 3H), (m, 1H), 2.64 (dd, J = 18.1, 7.5 Hz, 1H), 2.42 (dddd, J = 8.9, 8.2, 6.2, 5.0 Hz, 2H), (m, 2H), (m, 1H). 13 C NMR (101 MHz, CDCl 3 ) δ (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s). HPLC: Chiralcel OD-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 90:10; flow rate:0.7 ml/min; retention time: 13.4 min (minor), 13.9 min (major). Measured ee value = 83% Total Total (S)-3-(naphthalen-2-yl)cyclopentan-1-one [7] 3s: [ ] 32.8 D (c 0.015, CHCl 3 ). [lit. [7]: [ ] D -38 (c 0.14, CHCl 3 )]. 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3H), 7.70 (s, 1H), (m, 3H), 3.63 (tt, J = 10.7, 6.9 Hz, 1H), (m, 1H), (m, 4H), (m, 1H). 13 C NMR (101 MHz, DMSO-d 6 ) δ (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s), (s). HPLC: Chiralpak AD-H Column (Particle Size: 5 μm, dimensions: 4.6 mm 250 mm); detected at 254 nm; n-hexane: 2-propanol = 95:5; flow rate: 1.0 ml/min; retention time: 9.9 min (major), 10.5 min. Measured ee value = 55%. Page S15

16 Total Total Page S16

17 References [1] Lee, A.; Kim, H. J. Org. Chem. 2016, 81, [2] Khiar, N.; Valdivia, V.; Salvador, A.; Chelouan, A.; Alcudia, A.; Fernndez. Adv. Synth. Catal. 2013, 355, [3] Zhao, Y. S.; Liu, J. K.; He, Z.-T.; Tao, J.-C.; Tian, P.; Lin, G. Q. Org. Biomol. Chem. 2016, 14, [4] Chen, Q.; Chen, C.; Guo, V; Xia, W. Chem. Commun. 2013, 49, [5] Dong, J.; Liu, Y.; Cui, Y. Chem. Commun. 2014, 50, [6] Liu, C. C.; Janmanchi, C.; Chen, C. C.; Wu, H. L. Eur. J. Org. Chem. 2012, 2012, [7] Chen, Q.; Li, L.; Zhou, G.; Ma, X.; Zhang, L.; Guo, F.; Luo, Y.; Xia, W. Chem. Asian J. 2016, 11, [8] Khiar, N.; Salvador, Á; Valdivia, V.; Chelouan, A.; Alcudia, A.; Álvarez, E.; Fernández, I. J. Org. Chem. 2013, 78, [9] Feng, X.; Wang, Y.; Wei, B.; Yang, J.; Du, H. Org. Lett. 2011, 13, [10] Berhal, F.; Esseiva, O.; Martin, C.-H.; Tone, H.; Genet, J.-P.; Ayad, T.; Ratovelomanana-Vidal, V. Org. Lett., 2011, 13, Page S17

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40 S O N (R)-N-cinnamyl-2-methyl-N-phenylpropane-2-sulfinamide Page S40

41 Inten.(x10,000,000) m/z N S O (R)-N-allyl-2-methyl-N-phenylpropane-2-sulfinamide Inten.(x1,000,000) m/z N S O (R)-N-([1,1'-biphenyl]-4-yl)-N-cinnamyl-2-methylpropane-2-sulfinamide Inten.(x1,000,000) m/z N S O (R)-N-([1,1'-biphenyl]-4-yl)-N-allyl-2-methylpropane-2-sulfinamide Page S41

42 Inten.(x10,000,000) m/z Page S42