SUPPLEMENTARY INFORMATION

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1 DOI: /NCHEM.1989 Cooperative activation of cyclobutanones and olefins leads to bridged ring systems by a catalytic [4+2] coupling Haye Min Ko and Guangbin Dong* Department of chemistry and biochemistry, University of Texas at Austin, Austin, Texas 78712, United States Table of Contents 1. General Information S-2 2. Experimental Procedure and Characterization Data S-2 3. References S X-Ray Data for 2a, 2f, 2i, 2n, 2q-i, 2q-ii, 8 and enamine 2o-i S Spectra S-34 NATURE CHEMISTRY 1

2 1. General Information Unless otherwise noted, all manipulations were carried out under an inert atmosphere in a nitrogen-filled glovebox or by standard Schlenk techniques. Dichloromethane (DCM), diethyl ether (Et 2 O), tetrahydrofuran (THF), and toluene (PhMe) were purified using a Pure-Solv MD-5 Solvent Purification System (Innovative Technology). All other reagents were used directly from the supplier without further purification. Analytical thin-layer chromatography (TLC) was carried out using 0.2 mm commercial silica gel plates (silica gel 60, F254, EMD chemical). The vials (1 dram, mm with PTFE lined cap attached) were purchased from Qorpak and dried in an oven overnight and cooled under a stream of nitrogen prior to use. Infrared spectra were recorded on a Nicolet 380 FTIR using neat thin film technique. High-resolution mass spectra (HRMS) were obtained on a Karatos MS9 and are reported as m/z (relative intensity). Accurate masses are reported for the molecular ion [M+Na] +, [M+H] +, or [M+]. Nuclear magnetic resonance spectra ( 1 H NMR and 13 C NMR) were recorded with a Varian Gemini ( 1 H at 400 MHz, 13 C at 100 MHz). For CDCl 3 solutions the chemical shifts are reported as parts per million (ppm) referenced to residual protium or carbon of the solvents; CHCl 3 δ H (7.26 ppm) and CDCl 3 δ C (77.16 ppm). Coupling constants are reported in Hertz (Hz). Data for 1 H NMR spectra are reported as follows: chemical shift (ppm, referenced to protium; s = singlet, d = doublet, t = triplet, q = quartet, quin = quintet, dd = doublet of doublets, td = triplet of doublets, ddd = doublet of doublet of doublets, m = multiplet, coupling constant (Hz), and integration). 2. Experimental Procedures and Characterization Data Trichloroacetyl chloride (0.10 ml, 0.72 mmol) was added in one portion to a suspension of 4-methyl-N,Nbis(2-methylallyl)benzenesulfonamide (100 mg, 0.36 mmol) 1 and zinc dust (80 mg, 1.08 mmol) in ether (4 ml). The reaction mixture was stirred under sonication for 6h. Then the reaction was diluted with ether and filtered through a pad of Celite. The residue was filtered again through a pad of silica gel to give a yellow oil, which was used directly without further purification. A solution of the yellow oil in acetic acid (10 ml) was added dropwise to a vigorously stirred suspension of zinc dust (80 mg, 1.08 mmol) at room temperature. After the addition, the reaction mixture was heated at 70 o C overnight. The mixture was allowed to cool to room temperature and then concentrated under reduced pressure to eliminate most acetic acid. The residue was dissolved in EtOAc (10 ml) and the organic solution was washed with sat. NaHCO 3 solution (2 30 ml) and brine (50 ml), and dried over MgSO 4. Then the solution was filtered, concentrated and purified with flash chromatography to obtain 1a (50 mg, 2 steps 46%, 56% brsm). R f = 0.5 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), 7.31 (d, J = 8.0 Hz, 2H), 4.88 (t, J = 21.6 Hz, 1H), 4.81 (s, 1H), 3.76 (s, 2H), 3.41 (s, 2H), (m, 2H), (m, 2H), 2.43 (s, 3H), 1.30 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.5, 167.7, 143.5, 140.1, 129.7, 127.3, 114.7, 57.5, 56.7, 55.3, 29.9, 24.4, 21.5, IR: v 2958, 2924, 2870, 1783, 1598, 1450, 1339, 1159, 1091, 911 cm -1 ; HRMS calcd. for C 17 H 24 NO 3 S + [M+H] + : Found: NATURE CHEMISTRY 2

3 3-chloro-2-methylprop-1-ene (9.5 ml, 95.7 mmol) was added in one portion to a suspension of N-benzyl- 4-methylbenzenesulfonamide (10 g, 38.3 mmol) 2, K 2 CO 3 (13 g, 95.7 mmol) and KI (12.5 g, 76.5 mmol) in acetone (200 ml). The reaction mixture was heated to reflux overnight. The reaction was then quenched with sat. NH 4 Cl solution (100 ml). The aqueous phase was extracted with EtOAc (2 80 ml) and the combined organic extracts were washed with brine (80 ml), dried over anhydrous Na 2 SO 4, filtered, and concentrated under reduced pressure to give a colorless residue. The residue was purified by column chromatography to give 11.8 g (97%) of S-1 as a bright yellow oil. R f = 0.6 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), 7.29 (d, J = 8.0 Hz, 2H), (m, 3H), (m, 2H), 4.81 (s, 1H), 4.70 (s, 1H), 4.32 (s, 2H), 3.68 (s, 2H), 2.43 (s, 3H), 1.52 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 143.2, 140.0, 137.5, 136.0, 129.6, 128.7, 128.3, 127.6, 127.2, 114.7, 53.4, 50.7, 21.5, IR: v 2973, 2919, 1598, 1455, 1339, 1159, 1098, 1013, 922, 900 cm -1 ; HRMS calcd. for C 18 H 21 NNaO 2 S + [M+Na] + : Found: Trichloroacetyl chloride (0.21 ml, 1.9 mmol) was added in one portion to a suspension of S-1 (300 mg, 0.95 mmol) and zinc dust (124 mg, 1.9 mmol) in ether (10 ml). The reaction mixture was stirred under sonication for 2h. Then the reaction was diluted with ether and filtered through a pad of celite. The residue was filtered again through a pad of silica gel to give a yellow oil, which was used directly without further purification. A solution of the yellow oil in acetic acid (10 ml) was added dropwise to a vigorously stirred suspension of activated Zn-Cu 3 (124 mg, 1.9 mmol) at room temperature. After the addition, the reaction mixture was heated at 70 o C overnight. The mixture was allowed to cool to room temperature and then concentrated under reduced pressure to eliminate most acetic acid. The residue was dissolved in EtOAc (10 ml) and the organic solution was washed with sat. NaHCO 3 solution (2 30 ml) and brine (50 ml), and dried over MgSO 4. The solution was then filtered, concentrated and purified with flash chromatography to obtain S-2 (144 mg, 2 steps 42%). R f = 0.4 (EtOAc/Hexane=1/4). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), 7.34 (d, J = 8.4 Hz, 2H), (m, 3H), (m, 2H), 4.38 (s, 2H), 3.43 (s, 2H), (m, 2H), 2.45 (s, 3H), (m, 2H), 1.20 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.5, 143.7, 136.6, 136.0, 129.9, 128.7, 128.0, 127.9, 127.3, 57.6, 57.3, 53.8, 29.8, 24.5, IR: v 2958, 2923, 2869, 1781, 1454, 1337, 1159, 1090, 1051, 921 cm -1 ; HRMS calcd. for C 20 H 24 NO 3 S + [M+H] + : Found: A 250-mL, round-bottomed flask equipped with a magnetic stirrer bar, was charged with S-2 (144 mg, 0.40 mmol) and Pd(OH) 2 /C (15 mg) under H 2 gas in acetic acid (20 ml) and 6M HCl (10 ml). The reaction mixture was stirred at room temperature overnight. The reaction was then filtered through a pad of Celite and concentrated to eliminate most acetic acid. The residue was dissolved in EtOAc (10 ml) and the organic solution was washed with sat. NaHCO 3 solution (2 30 ml) and brine (50 ml), dried over MgSO 4. The resulting solution was filtered, concentrated and purified by flash chromatography to obtain S-3 (97 mg, 90%). R f = 0.2 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), 7.33 (d, J = 8.0 Hz, 2H), (m, 1H), 3.08 (d, J = 7.2 Hz, 2H), (m, 2H), (m, 2H), 2.44 (s, 3H), 1.32 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.2, 143.7, 136.7, 129.9, 127.0, 55.9, 52.0, 29.3, 24.2, IR: v 3282, 2959, 2923, 1778, 1598, 1450, 1413, 1329, 1160, 1093 cm -1 ; HRMS calcd. for C 13 H 18 NO 3 S + [M+H] + : Found: NATURE CHEMISTRY 3

4 Trichloroacetyl chloride (1.00 ml, 8.56 mmol) was added in one portion to a suspension of S-5 (939 mg, 4.28 mmol) 4 and zinc dust (560 mg, 8.56 mmol) in ether (10 ml). The reaction mixture was stirred under sonication for 2h. The reaction was diluted with ether and filtered through a pad of Celite. The residue was filtered again through a pad of silica gel to give a yellow oil, which was used directly without further purification. A solution of the yellow oil in acetic acid (20 ml) was added dropwise to a vigorously stirred suspension of activated Zn-Cu 3 (560 mg, 8.56 mmol) at room temperature. After the addition, the reaction mixture was heated at 70 o C overnight. The mixture was allowed to cool to room temperature and then concentrated under reduced pressure to eliminate most acetic acid. The residue was dissolved in EtOAc (10 ml) and the organic solution was washed with sat. NaHCO 3 solution (2 30 ml) and brine (50 ml), and dried over MgSO 4. The resulting solution was filtered, concentrated and purified with flash chromatography to obtain S-6 (532 mg, 2 steps 48%). R f = 0.6 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 5H), 4.57 (s, 2H), 3.74 (s, 3H), 3.54 (brs, 2H), (m, 2H), (m, 2H), 1.33 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.8, 206.4, 157.9, 137.2, 128.9, 128.7, 128.5, 127.5, 126.8, 57.2, 55.2, 54.2, 53.0, 51.5, 30.5, IR: v 2957, 2927, 1773, 1701, 1474, 1406, 1228, 1144, 1077, 968 cm -1 ; HRMS calcd. for C 15 H 19 NNaO 3 + [M+Na] + : Found: A 250-mL, round-bottomed flask equipped with a magnetic stirrer bar, was charged with S-6 (240 mg, 0.92 mmol) and Pd(OH) 2 /C (30 mg) under H 2 gas in acetic acid (30 ml) and 6M HCl (20 ml). The reaction mixture was stirred at room temperature overnight. Then the reaction was filtered through a pad of Celite and evacuated to eliminate most acetic acid. The residue was dissolved in EtOAc (10 ml) and the organic solution was washed with sat. NaHCO 3 solution (2 30 ml) and brine (50 ml), dried over MgSO 4. Then the solution was filtered, concentrated and purified with flash chromatography to obtain S-7 (137 mg, 88%). R f = 0.2 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 5.02 (brs, 1H), 3.67 (s, 3H), 3.39 (d, J = 6.4 Hz, 2H), 2.97 (d, J = 19.6 Hz, 2H), (m, 2H), 1.33 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.4, 157.6, 55.9, 52.3, 49.6, 30.2, IR: v 3340, 2956, 2921, 1781, 1711, 1546, 1250, 1192, 1147, 1012 cm -1 ; HRMS calcd. for C 8 H 13 NNaO 3 + [M+Na] + : Found: NaH (440 mg, 10.9 mmol) was added to a solution of methyl benzylcarbamate (1.5 g, 9.08 mmol) 5 in DMF (50 ml) at 0 C. After 30 min, alkyl mesylate (1.8 g, 10.9 mmol) was added to the resulting white suspension and the reaction mixture was stirred at ambient temperature for 2h. The reaction was carefully quenched with water (50 ml), the product was extracted with EtOAc (3x40 ml), and the combined organic solution was washed with brine (50 ml), dried with MgSO 4, filtered and evaporated. Flash chromatography of the residue gave the desired product S-8 as a colorless liquid (1.73 g, 82%). R f = 0.5 (EtOAc/Hexane=1/4). 1 H NMR (400 MHz, CDCl 3 ): (m, 5H), 4.91 (s, 1H), 4.80 (s, 1H), 4.43 (d, J = 16.8 Hz, 2H), (m, 5H), (brs, 2H), 1.05 (t, J = 6.8 Hz, 3H). 13 C NATURE CHEMISTRY 4

5 NMR (100 MHz, CDCl 3 ): 157.4, 157.2, 146.1, 137.6, 128.5, 128.4, 128.1, 127.4, 127.3, 110.3, 109.7, 52.8, 50.7, 50.1, 49.2, 48.6, 26.2, IR: v 2964, 2925, 1706, 1469, 1405, 1245, 1119, 952, 903, 700 cm -1 ; HRMS calcd. for C 14 H 19 NO 2 + [M+H] + : Found: Trichloroacetyl chloride (1.00 ml, 8.58 mmol) was added in one portion to a suspension of S-8 (1 g, 4.29 mmol) and zinc dust (560 mg, 8.58 mmol) in ether (10 ml). The reaction mixture was stirred under sonication for 2h. Then the reaction was diluted with ether and filtered through a pad of celite. The residue was filtered again through a pad of silica gel to give a yellow oil, which was used directly without further purification. A solution of the yellow oil in acetic acid (20 ml) was added dropwise to a vigorously stirred suspension of activated Zn-Cu 3 (560 mg, 8.58 mmol) at room temperature. After the addition, the reaction mixture was heated at 70 o C overnight. The mixture was allowed to cool to room temperature and then concentrated under reduced pressure to eliminate most acetic acid. The residue was dissolved in EtOAc (20 ml) and the organic solution was washed with sat. NaHCO 3 solution (2 30 ml) and brine (50 ml), and dried over MgSO 4. Then the solution was filtered, concentrated and purified with flash chromatography to obtain S-9 (689 mg, 2 steps 58%). R f = 0.2 (EtOAc/Hexane=1/4). 1 H NMR (400 MHz, CDCl 3 ): (m, 3H), 7.16 (brs, 2H), 4.54 (s, 2H), 3.73 (s, 3H), 3.51 (brs, 2H), 2.98 (brs, 2H), (m, 2H), 1.66 (q, J = 7.3 Hz, 2H), 0.94 (t, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.9, 158.0, 137.1, 128.8, 127.5, 126.8, 54.6, 53.0, 52.1, 51.4, 34.2, 29.8, 9.1. IR: v 2961, 2925, 1784, 1702, 1472, 1453, 1407, 1238, 1139, 955 cm -1 ; HRMS calcd. for C 16 H 21 NO 3 + [M+H] + : Found: A 250-mL, round-bottomed flask equipped with a magnetic stirrer bar, was charged with S-9 (357 mg, 1.30 mmol) and Pd(OH) 2 /C (30 mg) under H 2 gas in acetic acid (20 ml) and 6M HCl (10 ml). The reaction mixture was stirred at room temperature overnight. Then the reaction was filtered through a pad of celite and evacuated to eliminate most acetic acid. The residue was dissolved in EtOAc (20 ml) and the organic solution was washed with sat. NaHCO 3 solution (2 30 ml) and brine (50 ml), dried over MgSO 4. Then the solution was filtered, concentrated and purified with flash chromatography to obtain S- 10 (182 mg, 76%). R f = 0.2 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 5.15 (s, 1H), 3.62 (s, 3H), 3.36 (d, J = 6.0 Hz, 2H), 2.84 (d, J = 19.6 Hz, 2H), (m, 2H), 1.63 (q, J = 7.5 Hz, 2H), 0.91 (t, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.8, 157.6, 53.9, 52.2, 46.3, 33.8, 29.3, 9.1. IR: v 3342, 2965, 1782, 1703, 1538, 1462, 1385, 1256, 1192, 1138 cm -1 ; HRMS calcd. for C 9 H 15 NNaO 3 + [M+Na] + : Found: To a solution of methylene cyclohexane (300 mg, 3.12 mmol) in CH 2 C1 2 (16 ml, passed through alumina) was added a solution of diimide (1.1g, 3.43 mmol) 6 in CH 2 Cl 2 (12 ml) while stirring in an icebath under nitrogen. The resulting solution was stirred at room temperature for 14h and then concentrated NATURE CHEMISTRY 5

6 to afford an oil. This crude sulfenamide was hydrolyzed by stirring at room temperature for 14h with a solution of K 2 CO 3 (2.4 g) in CH 3 OH/ H 2 O (12 ml/ 8 ml). The residue was dissolved in ether (30 ml) and the organic phase was washed with sat. NaOH solution (20 ml) and brine (20 ml). The ether solution was dried over MgSO 4 and evaporated. Flash chromatography of the residue gave the desired product S-11 as a white solid (590 mg, 75%). R f = 0.5 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), (m, 1H), (m, 2H), 4.72 (brs, 1H), 4.70 (d, J = 0.8 Hz, 1H), 4.66 (s, 1H), 3.77 (td, J = 8.8, 3.9 Hz, 1H), (m 1H), (m, 1H), (m, 1H), (m, 1H), (m, 1H), (m, 3H). 13 C NMR (100 MHz, CDCl 3 ): 147.4, 141.1, 132.5, 128.9, 127.0, 107.7, 56.3, 35.7, 34.0, 27.2, IR: v 3275, 2932, 2856, 1449, 1321, 1165, 1094, 966, 898, 756 cm -1 ; HRMS calcd. for C 13 H 17 NNaO 2 S + [M+Na] + : Found: NaH (60 mg, 1.43 mmol) was added to a solution of N-(2-methylenecyclohexyl)benzenesulfonamide (S- 11, 300 mg, 1.19 mmol) in DMF (10 ml) at 0 C. After 30 min, Benzyl bromide (0.22 ml, 1.8 mmol) was added to the resulting white suspension and the reaction mixture was stirred at ambient temperature for overnight. The reaction was carefully quenched with water (25 ml), the product was extracted with EtOAc (3x25 ml), and the organic solution was washed with brine (25 ml), dried with MgSO 4, filtered and evaporated. Flash chromatography of the residue gave the desired product as a white solid (355 mg, 96%). R f = 0.3 (EtOAc/Hexane=1/4). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), (m, 1H), (m, 2H), (m, 2H), (m, 3H), 4.88 (d, J = 16.8 Hz, 1H), 4.69 (s, 1H), (m, 1H), 4.42 (d, J = 16.8 Hz, 1H), 4.29 (d, J = 1.2 Hz, 1H), (m, 1H), (m, 1H), (m, 3H), (m, 2H), (m, 1H). 13 C NMR (100 MHz, CDCl 3 ): 144.9, 141.3, 138.7, 132.2, 128.7, 128.2, 127.4, 127.1, 126.9, 108.0, 62.1, 48.9, 35.5, 34.1, 26.7, IR: v 3063, 2934, 2859, 1447, 1333, 1165, 1046, 1028, 924, 786 cm -1 ; HRMS calcd. for C 20 H 23 NNaO 2 S + [M+Na] + : Found: Trichloroacetyl chloride (1.00 ml, 8.78 mmol) was added in one portion to a suspension of S-12 (1.5 g, 4.39 mmol) and zinc dust (580 mg, 8.78 mmol) in ether (30 ml). The reaction mixture was stirred under sonication for 2h. Then the reaction was diluted with ether and filtered through a pad of Celite. The residue was filtered again through a pad of silica gel to give a yellow oil, which was used directly without further purification. A solution of the yellow oil in acetic acid (60 ml) was added dropwise to a vigorously stirred suspension of activated Zn-Cu 3 (580 mg, 8.78 mmol) at room temperature. After the addition, the reaction mixture was heated at 70 o C overnight. The mixture was allowed to cool to room temperature and then concentrated under reduced pressure to eliminate most acetic acid. The residue was dissolved in EtOAc (30 ml) and the organic solution was washed with sat. NaHCO 3 solution (2 40 ml) and brine (50 ml), and dried over MgSO 4. Then the solution was filtered, concentrated and purified with flash chromatography to obtain S-13 (1.06 g, 2 steps 63%). R f = 0.4 (EtOAc/Hexane=1/4). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), (m, 1H), (m, 2H), (m, 5H), 4.74 (d, J = 16.8 Hz, 1H), (m, 1H), 3.98 (d, J = 16.4 Hz, 1H), 3.76 (d, J = 18.0 Hz, 1H), 2.47 (dd, J = 17.8, 3.8 Hz, 1H), (m, 2H), (m, 4H), (m, 2H), (m, 2H). 13 C NMR (100 MHz, CDCl 3 ): 207.0, 139.6, 138.1, 132.9, 129.3, 129.0, 127.8, 127.4, 127.1, 63.0, 55.6, 51.3, 39.0, 35.5, 28.0, 26.5, IR: v 2929, 2857, 1780, 1446, 1339, 1166, 1090, 1023, 973, 736 cm -1 ; HRMS calcd. for C 22 H 25 NNaO 3 S + [M+Na] + : Found: A 250-mL, round-bottomed flask equipped with a magnetic stirrer bar, was charged with S-13 (298 mg, 0.78 mmol) and Pd/C (15 mg) under H 2 gas in acetic acid (20 ml) and isopropyl alcohol (20 ml). The NATURE CHEMISTRY 6

7 reaction mixture was stirred at 50 o C overnight. The reaction was filtered through a pad of Celite and evacuated to eliminate most acetic acid. The residue was dissolved in EtOAc (20 ml) and the organic solution was washed with sat. NaHCO 3 solution (2 30 ml) and brine (50 ml), dried over MgSO 4. The resulting solution was filtered, concentrated and purified with flash chromatography to obtain S-14 (34 mg, 15%, 75% brsm). R f = 0.3 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 7.89 (d, J = 7.6 Hz, 2H), (m, 3H), 5.00 (brs, 1H), 3.30 (td, J = 9.1, 3.2 Hz, 1H), 3.17 (d, J = 18.4 Hz, 1H), (m, 1H), (m, 2H), (m, 1H), (m, 7H). 13 C NMR (100 MHz, CDCl 3 ): 207.3, 140.6, 132.9, 129.3, 126.9, 57.4, 55.2, 35.9, 34.6, 30.1, 29.7, IR: v 3273, 2931, 1778, 1447, 1327, 1165, 1074, 934, 757, 721 cm -1 ; HRMS calcd. for C 15 H 19 NNaO 3 S + [M+Na] + : Found: Trichloroacetyl chloride (0.42 ml, 3.73 mmol) was added in one portion to a suspension of diethyl 2,2- bis(2-methylallyl)malonate (500 mg, 1.86 mmol) 7 and zinc dust (250 mg, 3.73 mmol) in ether (10 ml). The reaction mixture was stirred under sonication for 2h. Then the reaction was diluted with ether and filtered through a pad of Celite. The residue was filtered again through a pad of silica gel to give a yellow oil, which was used directly without further purification. A solution of the yellow oil in acetic acid (15 ml) was added dropwise to a vigorously stirred suspension of activated Zn-Cu 3 (250 mg, 3.73 mmol) at room temperature. After the addition, the reaction mixture was heated at 70 o C overnight. The mixture was allowed to cool to room temperature and then concentrated under reduced pressure to eliminate most acetic acid. The residue was dissolved in EtOAc (10 ml) and the organic solution was washed with sat. NaHCO 3 solution (2 30 ml) and brine (50 ml), and dried over MgSO 4. The resulting solution was filtered, concentrated and purified with flash chromatography to obtain 1o (256 mg, 2 steps 44%). R f = 0.5 (EtOAc/Hexane=1/4). 1 H NMR (400 MHz, CDCl 3 ): 4.84 (s, 1H), 4.72 (s, 1H), (m, 4H), (m, 2H), 2.74 (s, 2H), (m, 2H), 2.45 (s, 2H), 1.68 (s, 3H), 1.28 (s, 3H), 1.26 (t, J = 7.4 Hz, 6H). 13 C NMR (100 MHz, CDCl 3 ): 207.9, 171.3, 141.0, 114.9, 61.4, 59.7, 56.3, 44.2, 42.7, 28.4, 24.9, 23.6, IR: v 2981, 1784, 1729, 1448, 1369, 1237, 1185, 1143, 1018, 899 cm -1 ; HRMS calcd. for C 17 H 26 O 5 + [M+H] + : Found: Allyl alcohols S-4b 8, S-4c~S-4d 9, S-4e 10, S-4f~S-4h 11, S-4g 12 synthesized according to the literature procedure. are known compounds and were General Procedure for Synthesis of Precursors A flame-dried schlenk flask, equipped with a magnetic stirrer bar, was charged with R CH 2 OH (1.0 equiv.), TEA (1.1 equiv.), and methanesulfonyl chloride (1.1 equiv.) in CH 2 Cl 2. The reaction mixture was NATURE CHEMISTRY 7

8 stirred at room temperature for 1h. When the reaction was finished, it was concentrated under reduced pressure. The residue was filtered through a pad of silica gel to give a yellow oil, which was used directly without further purification. The yellow oil was added to a suspension of S-3 (100 mg, 0.37 mmol) and Cs 2 CO 3 (146 mg, 0.45 mmol) in DMF (15 ml) at room temperature. The reaction mixture was heated at 50 o C and monitored by TLC. When the reaction was finished, the reaction was quenched with sat. NH 4 Cl solution (20 ml). The aqueous phase was extracted with EtOAc (2 15 ml) and the combined organic extracts were washed with brine (20 ml), dried over anhydrous NaSO 4, filtered, and concentrated under reduced pressure to give a colorless residue. The residue was purified by column chromatography to yield the alkylation product. Using general procedure, 1b was synthesized as a yellow oil in 97% yield from cyclobutanone S-3 and S- 4b. R f = 0.7 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 7.68 (d, J = 8.0 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H), 4.90 (d, J = 0.8 Hz, 1H), 4.82 (d, J = 0.8 Hz, 1H), 3.75 (s, 2H), 3.38 (s, 2H), (m, 2H), (m, 2H), 2.41 (s, 3H), 1.87 (q, J = 7.5 Hz, 2H), 1.27 (s, 3H), 0.97 (t, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.6, 145.5, 143.5, 136.7, 129.7, 127.3, 112.3, 57.5, 57.0, 54.7, 29.9, 26.0, 24.4, 21.5, IR: v 2963, 2925, 2875, 1773, 1654, 1598, 1458, 1341, 1184, 654 cm -1 ; HRMS calcd. for C 18 H 26 NO 3 S + [M+H] + : Found: Using general procedure, 1c was synthesized as a colorless oil in 80% yield from cyclobutanone S-3 and S-4e. R f = 0.8 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 7.70 (d, J = 8.0 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 5.20 (d, J = 1.2 Hz, 1H), 4.94 (d, J = 1.2 Hz, 1H), 3.86 (s, 4H), 3.44 (s, 2H), (m, 2H), (m, 2H), 2.43 (s, 3H), 1.32 (s, 3H), 0.87 (s, 9H), 0.01 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ): 206.4, 143.6, 142.8, 136.8, 129.7, 127.3, 113.7, 64.0, 57.5, 56.7, 51.5, 30.0, 25.8, 24.4, 21.5, 18.3, IR: v 2954, 2928, 2856, 1786, 1598, 1472, 1388, 1341, 1252, 1161 cm -1 ; HRMS calcd. for C 23 H 38 NO 4 SSi + [M+H] + : Found: Using general procedure, 1d was synthesized as a yellow oil in 87% yield from cyclobutanone S-3 and S- 4c. R f = 0.5 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 7.68 (d, J = 8.0 Hz, 2H), 7.29 (d, J = 8.4 Hz, 2H), 4.90 (s, 1H), 4.77 (s, 1H), 3.79 (s, 2H), 3.39 (s, 2H), (m, 2H), (m, 2H), 2.41 (s, 3H), 2.12 (quin, J = 6.9 Hz, 1H), 1.28 (s, 3H), 0.98 (d, J = 7.2 Hz, 6H). 13 C NMR (100 MHz, CDCl 3 ): 206.6, 149.6, 143.5, 136.7, 129.7, 127.4, 110.7, 57.6, 57.2, 53.6, 30.9, 29.9, 24.4, 21.52, NATURE CHEMISTRY 8

9 IR: v 2961, 1773, 1597, 1490, 1341, 1158, 1090, 1053, 913, 816 cm -1 ; HRMS calcd. for C 19 H 28 NO 3 S + [M+H] + : Found: Using general procedure, 1e was synthesized as a yellow oil in 97% yield from cyclobutanone S-3 and S- 4d. R f = 0.7 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 7.70 (d, J = 8.0 Hz, 2H), 7.30 (d, J = 7.6 Hz, 2H), 4.94 (s, 1H), 4.79 (s, 1H), 3.79 (s, 2H), 3.42 (s, 2H), (m, 2H), (m, 2H), 2.43 (s, 3H), 2.10 (quin, J = 8.4 Hz, 1H), (m, 6H), 1.31 (s, 3H), (m, 2H). 13 C NMR (100 MHz, CDCl 3 ): 206.7, 147.2, 143.5, 136.7, 129.7, 127.4, 110.5, 57.6, 57.1, 54.5, 43.1, 31.4, 29.9, 24.7, 24.5, IR: v 2954, 2869, 1781, 1723, 1672, 1448, 1387, 1340, 1163, 1091 cm -1 ; HRMS calcd. for C 21 H 29 NNaO 3 S + [M+Na] + : Found: Using general procedure, 1f was synthesized as a colorless oil in 80% yield from cyclobutanone S-3 and Allyl bromide. R f = 0.6 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), (m, 2H), (m, 1H), (m, 2H), (m, 2H), 3.41 (s, 2H), (m, 2H), (m, 2H), 2.44 (s, 3H), 1.36 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.3, 143.6, 136.9, 132.6, 129.8, 127.2, 119.7, 57.3, 55.3, 51.7, 30.1, 24.6, IR: v 2961, 2925, 1782, 1597, 1494, 1450, 1341, 1159, 1091, 905 cm -1 ; HRMS calcd. for C 16 H 22 NO 3 S + [M+H] + : Found: Using general procedure, 1h was synthesized as a white solid in 98% yield from cyclobutanone S-3 and S- 4f. R f = 0.5 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), (m, 7H), 5.49 (d, J = 1.2 Hz, 1H), 5.19 (s, 1H), 4.22 (s, 2H), 3.41 (s, 2H), (m, 2H), (m, 2H), 2.45 (s, 3H), 1.22 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.6, 143.7, 142.3, 138.3, 136.1, 129.8, 128.6, 128.2, 127.5, 126.1, 115.9, 57.6, 57.1, 53.5, 29.8, 24.4, IR: v 2924, 1774, 1629, 1597, 1493, 1444, 1341, 1241, 1162, 1051 cm -1 ; HRMS calcd. for C 22 H 26 NO 3 S + [M+H] + : Found: NATURE CHEMISTRY 9

10 Using general procedure, 1i was synthesized as a white solid in 85% yield from cyclobutanone S-3 and S- 4g. R f = 0.6 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 7.71 (d, J = 8.0 Hz, 2H), 7.32 (d, J = 8.8 Hz, 4H), (m, 2H), 5.41 (s, 1H), 5.08 (s, 1H), 4.17 (s, 2H), 3.80 (s, 3H), 3.38 (s, 2H), (m, 2H), (m, 2H), 2.44 (s, 3H), 1.20 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.8, 159.6, 143.7, 141.6, 135.9, 130.5, 129.8, 127.5, 127.3, 114.5, 113.9, 57.6, 57.1, 55.3, 53.9, 29.8, 24.5, IR: v 2924, 1773, 1607, 1512, 1459, 1341, 1251, 1032, 903, 836 cm -1 ; HRMS calcd. for C 23 H 27 NNaO 4 S + [M+Na] + : Found: Using general procedure, 1j was synthesized as a yellow solid in 68% yield from cyclobutanone S-3 and S-4h. R f = 0.7 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 7.69 (d, J = 8.4 Hz, 2H), (m, 4H), (m, 2H), 5.44 (s, 1H), 5.18 (s, 1H), 4.17 (s, 2H), 3.38 (s, 2H), (m, 2H), (m, 2H), 2.44 (s, 3H), 1.20 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.5, 163.9, 161.4, 143.8, 141.5, 135.9, 134.3, 134.2, 129.8, 128.0, 127.9, 127.5, 116.1, 115.6, 115.4, 57.6, 57.2, 53.8, 29.8, 24.4, IR: v 2959, 2925, 2870, 1718, 1601, 1510, 1453, 1339, 1231, 1161 cm -1 ; HRMS calcd. for C 22 H 24 FNNaO 3 S + [M+Na] + : Found: Using general procedure, the alkylation product was synthesized as a white solid in 90% yield from cyclobutanone S-3 and 1-Bromo-2-butyne. R f = 0.6 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 7.71 (dd, J = 8.2, 1.4 Hz, 2H), 7.29 (d, J = 7.2 Hz, 2H), 4.07 (d, J = 2.4 Hz, 2H), 3.40 (s, 2H), (m, 2H), (m, 2H), 2.42 (s, 3H), 1.52 (s, 3H) 1.37 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.4, 143.5, 135.8, 129.3, 127.9, 82.9, 71.1, 57.4, 54.2, 37.9, 29.3, 24.2, 21.5, 3.2. IR: v 2960, 2921, 1781, 1653, 1559, 1457, 1347, 1160, 1091, 557 cm -1 ; HRMS calcd. for C 17 H 21 NNaO 3 S + [M+Na] + : Found: The white solid (100 mg, 0.31mmol) was added to a suspension of 10% Pd on BaSO 4 (21 mg, 0.02 mmol) and quinoline (2.6 mg, 0.02mmol) in EtOH (15 ml) under H 2 at room temperature. The reaction mixture was stirred for 2h. When the reaction was finished, the reaction was quenched with sat. NH 4 Cl solution (20 ml). The aqueous phase was extracted with EtOAc (2 15 ml) and the combined organic extracts were washed with brine (20 ml), dried over anhydrous NaSO 4, filtered, and concentrated under reduced pressure to give a colorless residue. The residue was purified by column chromatography to yield 1l (99 mg, 98%). R f = 0.7 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 7.68 (d, J = 8.4 Hz, 2H), 7.29 (d, J = 7.6 Hz, 2H), (m, 1H), (m, 1H), 3.92 (d, J = 6.4 Hz, 2H), 3.38 (s, 2H), (m, 2H), (m, 2H), 2.42 (s, 3H), 1.55 (d, J = 8.4 Hz, 3H), 1.37 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.5, 143.5, 136.9, 129.8, 128.4, 127.3, 124.7, 57.1, 55.5, 45.8, 30.0, 24.6, 21.5, IR: v 2960, 2925, NATURE CHEMISTRY 10

11 2869, 1782, 1598, 1450, 1340, 1159, 1052, 917 cm -1 ; HRMS calcd. for C 17 H 23 NNaO 3 S + [M+Na] + : Found: Using general procedure, 1m was synthesized as a colorless oil in 75% yield from cyclobutanone S-3 and S-4i. R f = 0.7 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 7.67 (d, J = 8.4 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), (m, 1H), (m, 1H), 3.79 (d, J = 6.8 Hz, 2H), 3.38 (s, 2H), (m, 2H), (m, 2H), 2.42 (s, 3H), 1.58 (d, J = 6.0 Hz, 3H), 1.33 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.5, 143.4, 137.0, 131.1, 129.6, 127.2, 125.1, 57.2, 54.9, 51.0, 30.1, 24.6, 21.4, IR: v 2962, 2924, 1783, 1598, 1450, 1337, 1159, 1091, 969, 917 cm -1 ; HRMS calcd. for C 17 H 23 NNaO 3 S + [M+Na] + : Found: Using general procedure, 1q was synthesized as a yellow oil in 79% yield from cyclobutanone S-14 and S-4a. R f = 0.5 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), (m, 1H), (m, 2H), 5.06 (s, 1H), 5.00 (s, 1H), (m, 3H), 3.39 (d, J = 17.6 Hz, 1H), 2.97 (d, J = 16.8 Hz, 1H), (m, 2H), 1.74 (s, 3H), (m, 4H), (m, 3H), 0.94 (d, J = 10.0 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ): 207.6, 142.0, 139.2, 132.9, 129.2, 127.2, 113.7, 62.6, 55.7, 51.2, 50.4, 39.1, 35.4, 27.7, 26.4, 23.0, IR: v 2929, 2856, 1780, 1446, 1341, 1168, 1090, 997, 905, 755 cm -1 ; HRMS calcd. for C 19 H 25 NNaO 3 S + [M+Na] + : Found: NaH (110 mg, 2.66 mmol) was added to a solution of S-7 (380 mg, 2.22 mmol) and Allyl bromide (0.23 ml, 2.66 mmol) in THF/DMF (20 ml, 1/1 v/v) at 0 C. The resulting white suspension was stirred at ambient temperature for 2h. The reaction was carefully quenched with water (25 ml), the product was extracted with EtOAc (3x25 ml), and the combined organic extracts were washed with brine (25 ml), dried with MgSO 4, filtered and evaporated. Flash chromatography of the residue gave the desired product as a colorless liquid (170 mg, 36%, 65% brsm). R f = 0.5 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 1H), (m, 2H), 3.92 (brs, 2H), 3.71 (s, 3H), 3.51 (s, 2H), 3.10 (brs, 2H), (m, 2H), 1.32 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 207.0, 157.9, 133.2, 117.3, 116.8, 57.0, 55.2, 54.4, 52.8, 51.1, 31.9, 30.6, 29.7, 29.6, 29.3, 24.6, 22.7, IR: v 2956, 2927, 1781, 1701, 1469, 1402, 1238, 1191, 995, 931 cm -1 ; HRMS calcd. for C 11 H 17 NNaO 3 + [M+Na] + : Found: NATURE CHEMISTRY 11

12 NaH (24 mg, 0.60 mmol) was added to a solution of S-10 (93 mg, 0.50 mmol) and 3-chloro-2-methylprop- 1-ene (0.12 ml, 0.6 mmol) in DMF (5 ml) at 0 C. The resulting white suspension was stirred at ambient temperature for 2h. The reaction was carefully quenched with water (10 ml), the product was extracted with EtOAc (3x15 ml), and the combined organic extracts were washed with brine (25 ml), dried with MgSO 4, filtered and evaporated. Flash chromatography of the residue gave the desired product as a yellow liquid (25 mg, 21%, 68% brsm). R f = 0.6 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 4.89 (s, 1H), 4.70 (s, 1H), 3.84 (brs, 2H), 3.69 (s, 3H), 3.49 (s, 2H), 3.02 (brs, 2H), (m, 2H), (m, 5H), 0.95 (t, J = 7.6 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ): 207.2, 158.0, 140.4, 112.0, 111.4, 54.5, 53.5, 52.9, 51.7, 50.8, 34.3, 29.8, 29.7, 19.9, 9.1. IR: v 2962, 2925, 1786, 1702, 1469, 1403, 1381, 1237, 1140, 897 cm -1 ; HRMS calcd. for C 13 H 21 NNaO 3 + [M+Na] + : Found: S-3 (30 mg, 0.11 mmol), vinyl acetate (5 ml), Pd(OAc) 2 (6.3 mg, 5 mol%), and IPr (1,3-bis(2,6-diisopropyl-phenyl)imidazol-2-ylidene (5.3 mg, 10 mol%) 13 were combined in a round-bottom flask equipped with a magnetic stir bar. The reaction mixture was stirred at room temperature open to air overnight. The solvents were removed and purification of the residue by column chromatography yielded the corresponding product (10 mg, 31%, 55% brsm). R f = 0.7 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 7.66 (d, J = 8.0 Hz, 2H), 7.32 (d, J = 8.4 Hz, 2H), 6.89 (dd, J = 15.8, 9.0 Hz, 1H), 4.49 (dd, J = 9.4, 1.8 Hz, 1H), 4.35 (dd, J = 15.6, 1.6 Hz, 1H), 3.46 (s, 2H), (m, 2H), (m, 2H), 2.43 (s, 3H), 1.35 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.7, 144.2, 135.2, 134.3, 129.9, 127.1, 96.4, 56.3, 51.9, 30.6, 25.5, IR: v 2960, 2926, 2870, 1782, 1628, 1459, 1353, 1324, 1232, 1167 cm -1 ; HRMS calcd. for C 15 H 19 NNaO 3 S + [M+Na] + : Found: NATURE CHEMISTRY 12

13 Supplementary Table 1- Selected optimization studies O Me O TsNH 2 Cl Me 3 steps 100 mol% N NH 2 Ts 3 Me N Rh Precatalyst Me 46% yield Ligand, Solvent N 1a Me 24 h Ts Me 2a Entry Catalyst Ligand/Additive Solvent Temp.( o C) Yield (%) * 1 20 mol% RhCl(PPh 3 ) 3 Toluene mol% [Rh(CO) 2 Cl] 2 Toluene mol% [Rh(CO) 2 (acac)] Toluene mol% [Rh(COE) 2 Cl] 2 Toluene mol% [Rh(1,5-hexadiene)Cl] 2 Toluene mol% [Rh(C 2 H 4 ) 2 Cl] 2 Toluene mol% [Rh(nbd)dppp]PF 6 10 mol% BHT Xylenes mol% [Rh(COD)Cl] 2 Toluene 130 < mol% [Rh(COD)Cl] 2 ClPh (34) mol% [Rh(COD)Cl] 2 10 mol% [Rh(COD)Cl] 2 10 mol% [Rh(COD)Cl] 2 20 mol% COD Xylenes (30) 1,4-Dioxane (51) 1,4-Dioxane (57) mol% [Rh(COD)Cl] 2 20 mol% P(C 6 F 5 ) 3 1,4-Dioxane (65) 10 mol% [Rh(COD)Cl] 2 10 mol% P(3,5-C 6 H 3 (CF 3 ) 2 ) 3 1,4-Dioxane (74) 10 mol% [Rh(COD)Cl] 2 22 mol% P(3,5-C 6 H 3 (CF 3 ) 2 ) 3 1,4-Dioxane mol% [Rh(COD)Cl] 2 22 mol% P(3,5-C 6 H 3 (CF 3 ) 2 ) 3 1,4-Dioxane (88) 5 mol% [Rh(C 24 mol% P(3,5-C 6 H 3 (CF 3 ) 2 ) 2 H 4 ) 2 Cl] 2 3 1,4-Dioxane mol% [Rh(C 2 H 4 ) 2 Cl] 2 24 mol% P(3,5-C 1,4-Dioxane H 3 (CF 3 ) 2 ) 3 * Isolated yield; numbers in parentheses are brsm yield. 20 mol% 3 was used with 71 h reaction time. no 3 was added. The reaction time was 48 h. Decarbonylation products were observed as an inseperable mixture. NATURE CHEMISTRY 13

14 Conditions for the Rh-catalyzed C C activation (Reaction was performed at 0.1~0.2 mmol scale at 0.1 M concentration): In a nitrogen filled glove box, a 1 dram vial was charged with 5 mol% [Rh(C 2 H 4 ) 2 Cl] 2, 24 mol% Tris[3,5- bis(trifluoromethyl)phenyl]phosphine and 100 mol% 2-amino-3-picoline or 10 mol% [Rh(C 2 H 4 ) 2 Cl] 2, 48 mol% Tris[3,5-bis(trifluoromethyl)phenyl]phosphine and 100 mol% 2-amino-3-picoline. A solution of starting material in dioxane (0.1 M) was added and the 1 dram vial was capped and the solution was maintained at 152 C for 24~48 h. The reaction was removed from the glove box and purified by flash chromatography. On a 0.1 mmol scale, 2a was obtained as a bright orange solid (28 mg, 87%). R f = 0.2 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 7.61 (d, J = 8.4 Hz, 2H), 7.32 (d, J = 8.0 Hz, 2H), 3.41 (dd, J = 11.6, 2.0 Hz, 2H), 2.43 (s, 3H), 2.32 (dd, J = 16.6, 2.6 Hz, 2H), 2.08 (s, 2H), (m, 2H), 1.58 (dt, J = 13.2, 2.0 Hz, 1H), (m, 1H), 0.98 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ): 206.6, 143.8, 133.1, 129.7, 127.9, 56.7, 51.6, 45.7, 34.5, 26.3, IR: v 2927, 2871, 1705, 1599, 1453, 1409, 1342, 1285, 936, 823 cm -1 ; HRMS calcd. for C 17 H 24 NO 3 S + [M+H] + : Found: On a 0.1 mmol scale, 2b was obtained as a white solid (27 mg, 81%). R f = 0.2 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), 7.30 (d, J = 8.0 Hz, 2H), 3.45 (dd, J = 11.2, 1.6 Hz, 1H), 3.40 (dd, J = 11.2, 1.6 Hz, 1H), 2.41 (s, 3H), (m, 2H), (m, 4H), 1.56 (dt, J = 13.1, 2.1 Hz, 1H), (m, 2H), 1.16 (dt, J = 13.3, 2.6 Hz, 1H), 0.97 (s, 3H), 0.84 (t, J = 7.8 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.9, 143.8, 133.1, 129.6, 127.9, 57.0, 55.4, 51.9, 48.8, 43.5, 37.3, 34.3, 32.2, 26.4, 21.6, 7.3. IR: v 2927, 2853, 1706, 1598, 1462, 1344, 1153, 1229, 1093, 1021 cm -1 ; HRMS calcd. for C 18 H 26 NO 3 S + [M+H] + : Found: On a 0.1 mmol scale, 2c was obtained as a colorless oil (28 mg, 63%, 86% brsm). R f = 0.4 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 7.60 (d, J = 8.0 Hz, 2H), 7.30 (d, J = 8.0 Hz, 2H), 3.43 (t, J = 10.2 Hz, 2H), 3.32 (dd, J = 13.0, 10.2 Hz, 2H), 2.41 (s, 3H), 2.30 (t, J = 14.4 Hz, 2H), (m, 4H), (m, 1H), (m, 1H), 0.99 (s, 3H), 0.83 (s, 9H), 0.01 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ): 206.7, 143.8, 132.9, 129.6, 128.0, 69.2, 56.9, 53.4, 52.1, 41.7, 40.6, 39.9, 34.1, 26.5, 25.8, 21.5, 18.2, IR: v 2928, 2855, 1711, 1472, 1346, 1259, 1229, 1156, 1092, 979 cm -1 ; HRMS calcd. for C 23 H 38 NO 4 SSi + [M+H] + : Found: NATURE CHEMISTRY 14

15 On a 0.1 mmol scale, 2d was obtained as a colorless oil (22 mg, 63%). R f = 0.2 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), 7.32 (d, J = 8.4 Hz, 2H), 3.58 (dt, J = 11.2, 2.0 Hz, 1H), (m, 1H), 2.43 (s, 3H), (m, 2H), (m, 4H), 1.62 (dt, J = 13.3, 2.1 Hz, 1H), 1.49 (quin, J = 6.9 Hz, 1H), 1.20 (dt, J = 13.2, 2.8 Hz, 1H), 0.99 (s, 3H), 0.89 (d, J = 7.2 Hz, 3H), 0.86 (d, J = 6.8 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ): 207.2, 143.8, 133.2, 129.6, 127.9, 56.9, 53.9, 52.0, 45.9, 41.8, 39.8, 34.9, 34.1, 26.5, 21.6, 16.8, IR: v 2960, 2872, 1711, 1598, 1466, 1345, 1163, 1092, 1033, 984 cm -1 ; HRMS calcd. for C 19 H 27 NNaO 3 S + [M+Na] + : Found: On a 0.1 mmol scale, 2e was obtained as a colorless oil (20 mg, 52%, 75% brsm). R f = 0.4 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), 7.32 (d, J = 8.0 Hz, 2H), 3.50 (dt, J = 11.1, 1.9 Hz, 1H), 3.40 (dt, J = 10.9, 1.9 Hz, 1H), 2.43 (s, 3H), (m, 2H), (m, 4H), (m, 6H), (m, 5H), 0.98 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 207.1, 143.8, 133.2, 129.6, 127.9, 57.0, 54.9, 52.1, 47.8, 47.0, 42.2, 39.3, 34.1, 29.7, 26.5, 26.2, 26.0, 25.3, IR: v 2925, 2868, 1707, 1598, 1458, 1346, 1166, 1092, 1037, 985 cm -1 ; HRMS calcd. for C 21 H 29 NNaO 3 S + [M+Na] + : Found: On a 0.1 mmol scale, 2f was obtained as a white solid (24 mg, 79%). R f = 0.2 (EtOAc/Hexane=1/1). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), 7.32 (d, J = 8.4 Hz, 2H), (m, 1H), 3.42 (dt, J = 11.6, 2.0 Hz, 1H), 2.43 (s, 3H), (m, 5H), (m, 2H), 1.74 (dd, J = 13.4, 1.8 Hz, 1H), 1.45 (dd, J = 13.2, 2.4 Hz, 1H), 0.97 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.5, 143.8, 133.1, 129.6, 128.0, 57.1, 52.6, 51.2, 44.7, 37.9, 34.0, 30.5, 16.7, IR: v 2924, 1774, 1629, 1597, 1493, 1460, 1341, 1241, 1163, 1051 cm -1 ; HRMS calcd. for C 16 H 22 NO 3 S + [M+H] + : Found: On a 0.1 mmol scale, 2g was obtained as a colorless oil (17 mg, 80%). R f = 0.1 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 3.66 (s, 3H), 2.86 (brs, 1H), 2.57 (brs, 1H), 2.36 (s, 3H), (m, 3H), NATURE CHEMISTRY 15

16 (m, 1H), (m, 1H), 1.25 (s, 1H), 1.00 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 208.4, 155.9, 55.3, 53.0, 52.6, 49.2, 44.8, 39.0, 35.3, 32.0, 29.7, IR: v 2953, 2925, 2855, 1703, 1453, 1410, 1286, 1271, 1219, 1137 cm -1 ; HRMS calcd. for C 11 H 17 NNaO 3 + [M+Na] + : Found: On a 0.1 mmol scale, 2h was obtained as a white solid (21 mg, 56%, 69% brsm). R f = 0.2 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), (m, 2H), (m, 5H), 3.83 (dt, J = 11.5, 2.1 Hz, 1H), 3.52 (dt, J = 11.3, 1.9 Hz, 1H), 2.86 (dt, J = 16.0, 2.4 Hz, 1H), 2.44 (dt, J = 16.1, 2.3 Hz, 1H), 2.40 (s, 3H), (m, 1H), (m, 2H), 2.00 (dt, J = 13.3, 2.1 Hz, 1H), 1.79 (dt, J = 13.2, 2.1 Hz, 1H), 1.09 (s, 3H), (m, 1H). 13 C NMR (125 MHz, CDCl 3 ): 205.5, 143.9, 143.7, 133.2, 129.7, 128.9, 127.8, 127.4, 125.0, 56.8, 56.6, 51.6, 51.0, 43.2, 40.9, 34.3, 26.6, IR: v 2954, 2925, 2852, 1707, 1598, 1499, 1457, 1346, 1234, 1166 cm -1 ; HRMS calcd. for C 22 H 25 NNaO 3 S + [M+Na] + : Found: On a 0.1 mmol scale, 2i was obtained as a white solid (27 mg, 66%, 78% brsm). R f = 0.2 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), (m, 2H), (m, 2H), (m, 2H), 3.80 (dt, J = 11.1, 2.1 Hz, 1H), 3.79 (s, 3H), 3.52 (dt, J = 11.5, 1.9 Hz, 1H), 2.85 (dt, J = 16.0, 2.4 Hz, 1H), (m, 4H), 2.35 (d, J = 16.0 Hz, 1H), 2.27 (dd, J = 11.6, 1.2 Hz, 1H), (m 2H), 1.97 (dt, J = 13.3, 2.0 Hz, 1H), 1.77 (dt, J = 13.2, 2.8 Hz, 1H), 1.09 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 205.8, 158.6, 143.9, 135.8, 133.1, 129.7, 127.8, 126.1, 114.1, 56.8, 56.7, 55.3, 51.6, 51.1, 43.3, 40.3, 34.3, 26.6, IR: v 2955, 2924, 2853, 1707, 1697, 1466, 1304, 1252, 1166, 1038 cm -1 ; HRMS calcd. for C 23 H 27 NNaO 4 S + [M+Na] + : Found: On a 0.1 mmol scale, 2j was obtained as a yellow solid (15 mg, 39%, 43% brsm). R f = 0.2 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), (m, 4H), (m, 2H), 3.81 (dt, J = 11.3, 1.9 Hz, 1H), (m, 1H), 2.85 (dt, J = 16.8, 4.8 Hz, 1H), 2.45 (dt, J = 16.3, 2.0 Hz, 1H), 2.41 (s, 3H), 2.35 (d, J = 16.0 Hz, 1H), 2.28 (dd, J = 11.6, 1.2 Hz, 1H), (m, 2H), 1.99 (dt, J = 13.2, 2.0 Hz, 1H), 1.77 (dt, J = 13.1, 2.7 Hz, 1H), 1.10 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 205.4, 144.0, 139.5, 133.1, 129.7, 127.8, 126.7, 126.6, 115.8, 115.6, 56.8, 56.6, 51.5, 51.0, 43.2, 40.5, 34.3, 26.5, IR: v 2925, 2851, 1707, 1598, 1512, 1459, 1345, 1231, 1167, 1092 cm -1 ; HRMS calcd. for C 22 H 24 FNNaO 3 S + [M+Na] + : Found: NATURE CHEMISTRY 16

17 On a 0.1 mmol scale, 2k was obtained as a colorless oil (18 mg, 76%). R f = 0.2 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 3.67 (s, 3H), 2.49 (brs, 2H), (m, 2H), (m, 2H), (m, 3H), (m, 3H), 1.01 (s, 3H), 0.90 (t, J = 7.6 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ): 208.7, 155.7, 55.1, 53.5, 53.0, 51.9, 48.7, 44.6, 38.6, 35.6, 32.1, 30.9, 29.7, 26.2, 7.3. IR: v 2956, 2925, 1719, 1701, 1459, 1411, 1364, 1291, 1101, 980 cm -1 ; HRMS calcd. for C 13 H 21 NO 3 + [M+H] + : Found: On a 0.1 mmol scale, 2l was obtained as a yellow oil (24 mg, 74%). R f = 0.2 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 7.60 (d, J = 7.2 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H), 3.78 (d, J = 10.4 Hz, 0.7H), 3.58 (d, J = 11.2 Hz, 0.3H), (m, 1H), (m, 3.6H), (m, 5H), 2.03 (brs, 0.4H), 1.89 (d, J = 14.0 Hz, 0.4H), 1.82 (d, J = 13.6 Hz, 0.8H), 1.75 (brs, 0.4H), 1.51 (d, J = 12.8 Hz, 0.8H), 1.26 (d, J = 11.6 Hz, 0.7H), 1.18 (dd, J = 7.8, 1.0 Hz, 1H), 1.12 (d, J = 6.0 Hz, 2H), 0.96 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 210.5, 208.1, 143.8, 143.7, 133.0, 132.9, 129.6, 127.9, 57.3, 57.1, 52.4, 52.1, 49.3, 47.7, 46.3, 45.9, 39.8, 37.0, 36.6, 35.0, 34.3, 33.2, 26.7, 26.6, 21.6, 18.1, IR: v 2954, 2926, 2871, 1706, 1598, 1459, 1345, 1280, 1166, 1093 cm -1 ; HRMS calcd. for C 17 H 23 NNaO 3 S + [M+Na] + : Found: On a 0.1 mmol scale, 2m was obtained as a yellow oil (15 mg, 46%). R f = 0.2 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 7.60 (d, J = 7.2 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H), 3.78 (d, J = 10.4 Hz, 0.7H), 3.58 (d, J = 11.2 Hz, 0.3H), (m, 1H), (m, 3.6H), (m, 5H), 2.03 (brs, 0.4H), 1.89 (d, J = 14.0 Hz, 0.4H), 1.82 (d, J = 13.6 Hz, 0.8H), 1.75 (brs, 0.4H), 1.51 (d, J = 12.8 Hz, 0.8H), 1.26 (d, J = 11.6 Hz, 0.7H), 1.18 (dd, J = 7.8, 1.0 Hz, 1H), 1.12 (d, J = 6.0 Hz, 2H), 0.96 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 210.5, 208.1, 143.8, 143.7, 133.0, 132.9, 129.6, 127.9, 57.3, 57.1, 52.4, 52.1, 49.3, 47.7, 46.3, 45.9, 39.8, 37.0, 36.6, 35.0, 34.3, 33.2, 26.7, 26.6, 21.6, 18.1, IR: v 2953, 2926, 2871, 1705, 1598, 1460, 1345, 1166, 1093, 960 cm -1 ; HRMS calcd. for C 17 H 23 NNaO 3 S + [M+Na] + : Found: NATURE CHEMISTRY 17

18 On a 0.1 mmol scale, 2n was obtained as a white solid (15 mg, 50%, 75% brsm). R f = 0.2 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), 7.32 (d, J = 8.4 Hz, 2H), (m, 1H), 3.24 (dd, J = 9.0, 1.4 Hz, 1H), 2.96 (dd, J = 9.0, 2.2 Hz, 1H), (m, 1H), (m, 1H), 2.44 (s, 3H), 2.30 (dt, J = 17.6, 2.4 Hz, 1H), 1.72 (d, J = 12.0 Hz, 1H) (m, 1H), 1.12 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 207.3, 143.7, 135.2, 129.8, 127.2, 59.2, 57.0, 54.0, 48.3, 42.3, 41.1, 23.3, IR: v 2958, 2925, 1717, 1456, 1338, 1164, 1140, 1093, 1048, 916 cm -1 ; HRMS calcd. for C 15 H 20 NO 3 S + [M+H] + : Found: On a 0.1 mmol scale, 2o was obtained as a colorless oil (17 mg, 54%, 81% brsm). R f = 0.4 (EtOAc/Hexane=1/3). 1 H NMR (400 MHz, CDCl 3 ): (m, 4H), 2.47 (dd, J = 14.8, 2.0 Hz, 2H), 2.35 (dd, J = 18.4, 2.4 Hz, 2H), 1.90 (d, J = 17.2 Hz, 2H), 1.66 (d, J = 13.2 Hz, 2H), 1.49 (dt, J = 7.7, 4.3 Hz, 1H), 1.37 (dt, J = 7.8, 4.3 Hz, 1H), 1.27 (t, J = 7.0 Hz, 3H), 1.20 (t, J = 7.0 Hz, 3H), 1.06 (s, 6H). 13 C NMR (100 MHz, CDCl 3 ): 211.4, 172.5, 170.9, 62.3, 62.0, 53.9, 51.9, 47.0, 41.5, 33.3, 31.9, 13.9, IR: v 2954, 2925, 1735, 1458, 1368, 1261, 1179, 1096, 1061, 864 cm -1 ; HRMS calcd. for C 17 H 26 O 5 Na + [M+Na] + : Found: On a 0.1 mmol scale, 2q-ii was obtained as a colorless oil (14 mg, 41%). R f = 0.5 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), (m, 3H), 3.91 (dd, J = 11.8, 2,6 Hz, 1H), 2.88 (d, J = 16.4 Hz, 1H), 2.64 (dd, J = 12.2, 3.8 Hz, 1H), 2.57 (dd, J = 11.6, 1.2 Hz, 1H), 2.43 (dt, J = 16.1, 2.3 Hz, 1H), 2.16 (d, J = 16.0 Hz, 1H), 2.09 (dd, J = 13.4, 3.4 Hz, 1H), (m, 9H), (m, 1H), 1.02 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 207.1, 140.7, 132.6, 129.0, 127.2, 67.3, 60.3, 51.9, 48.9, 45.5, 39.0, 38.8, 34.4, 26.5, 26.3, 25.8, IR: v 2925, 2852, 1701, 1446, 1348, 1325, 1090, 1073, 993, 885 cm -1 ; HRMS calcd. for C 19 H 25 NO 3 S + [M] + : Found: On a 0.1 mmol scale, 2q-i was obtained as a colorless oil (14 mg, 41%). R f = 0.4 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), (m, 1H), (m, 2H), 3.67 (dd, J = NATURE CHEMISTRY 18

19 12.0, 4,4 Hz, 1H), 3.11 (dd, J = 12.2, 1.8 Hz, 1H), 2.75 (d, J = 12.0 Hz, 1H), 2.27 (dd, J = 16.2, 2.6 Hz, 1H), (m, 4H), 1.71 (dd, J = 13.0, 3.0 Hz, 1H), (m, 8H), 1.00 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 206.1, 139.4, 132.8, 128.9, 127.7, 60.3, 54.4, 52.4, 50.9, 39.0, 37.7, 37.6, 34.6, 26.5, 25.0, 23.6, IR: v 2927, 2856, 1706, 1447, 1342, 1232, 1165, 1090, 1036, 978 cm -1 ; HRMS calcd. for C 19 H 25 NO 3 S + [M] + : Found: A solution of peroxytrifluoroacetic acid and trifluoroacetic acid in CH 2 C1 2 was prepared by adding a 60% solution of H 2 O 2 (0.5 ml, mmol) to a vigorously stirred solution of trifluoroacetic anhydride (3.5 ml, 24.8 mmol) in CH 2 Cl 2 (46 ml) cooled to 0 o C. After stirring for 10 min, the solution was 0.2 M in trifluoroperacetic acid and 0.7 M in trifluoroacetic acid. 14 This solution (1.45 ml, 0.29 mmol) was slowly added to a vigorously stirred slurry containing the 2a (55 mg, 0.17 mmol) and Na 2 HPO 4 (681 mg, 4.79 mmol) in CH 2 Cl 2 (20 ml) at 0 o C. Stirring was continued at 50 o C overnight. Water was added and the aqueous phase was extracted with CH 2 Cl 2 (3x20 ml). The combined organic phases were washed with sat. NaHCO 3 solution (50 ml), dried by Na 2 SO 4, filtered, and concentrated. Flash chromatography of the residue afforded the desired product 5 (25 mg, 40% 95% brsm). The mechanism for forming the α- chloroketone is unclear, while other ketone α-halogenation reactions, such as use of NBS, gave a complex mixture. Attempt to obtain the Baeyer Villiger oxidation product (7) was unsuccessful. R f = 0.5 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): (m, 2H), 7.33 (d, J = 7.6 Hz, 2H), 3.91 (s, 1H), 3.56 (dt, J = 11.6, 2.0 Hz, 1H), 3.43 (dt, J = 11.2, 2.0 Hz, 1H), 2.66 (dd, J = 16.0, 1.2 Hz, 1H), 2.44 (s, 3H), 2.26 (d, J = 11.6 Hz, 1H), (m, 1H), (m, 2H), 1.25 (d, J = 2.8 Hz, 1H), 1.05 (s, 3H), 1.00 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 199.4, 144.2, 132.7, 129.8, 127.9, 66.6, 56.8, 55.5, 46.0, 39.5, 38.0, 34.6, 25.9, 23.2, IR: v 2958, 2926, 1723, 1464, 1348, 1168, 1091, 962, 817, 785 cm -1 ; HRMS calcd. for C 17 H 22 ClNO 3 S + [M+H] + : Found: A methanolic solution of NaOMe (0.2 ml) was added at 0 o C to a solution of 5 (14 mg, 0.04 mmol) in MeOH (5 ml) and the mixture was stirred for 1h at 100 o C. 15 Then the reaction was quenched with sat. NH 4 Cl solution (10 ml). The aqueous phase was extracted with EtOAc (2 10 ml) and the combined organic extracts were washed with brine (10 ml), dried over NaSO 4, filtered, and concentrated under reduced pressure to give a colorless residue. The residue was purified by column chromatography to give 10.6 mg (78%) of 6 as a bright yellow oil. R f = 0.8 (EtOAc/Hexane=1/2). 1 H NMR (400 MHz, CDCl 3 ): 7.63 (d, J = 8.4 Hz, 2H), 7.32 (d, J = 8.0 Hz, 2H), 3.65 (s, 3H), (m, 1H), (m, 1H), 2.83 (dd, J = 8.4, 5.6 Hz, 1H), 2.43 (s, 3H), (m, 2H), (m, 1H), (m, 1H), 1.68 (dt, J = 11.3, 1.9 Hz, 1H), 1.06 (s, 3H), 0.93 (s, 3H), 0.84 (d, J = 11.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ): 176.6, 143.4, 133.5, 129.6, 127.5, 57.8, 56.6, 51.4, 50.3, 48.2, 44.4, 40.3, 40.0, 22.9, 21.5, IR: v 2953, 2931, 1733, 1599, 1456, 1436, 1343, 1163, 1093, 992 cm -1 ; HRMS calcd. for C 18 H 25 NO 4 S + [M+H] + : Found: NATURE CHEMISTRY 19

20 Hydroxylamine hydrochloride (6.5 mg, 0.09 mmol) was added in one portion to a solution of 2a (25 mg, 0.08 mmol) in pyridine/etoh/water (2/ 1/ 1 ml). The reaction mixture was heated to reflux overnight. The reaction was quenched with sat. NH 4 Cl solution (10 ml). The aqueous phase was extracted with EtOAc (2 10 ml) and the combined organic extracts were washed with brine (10 ml), dried over NaSO 4, filtered, and concentrated under reduced pressure to give a colorless residue. The residue was purified by column chromatography to give 26 mg (99%) of 2a-i as a bright orange solid. R f = 0.4 (EtOAc/Hexane=1/1). 1 H NMR (400 MHz, CDCl 3 ): 7.61 (d, J = 8.0 Hz, 2H), 7.31 (d, J = 7.6 Hz, 2H), 3.51 (d, J = 10.8 Hz, 1H), 3.43 (d, J = 11.6 Hz, 1H), 3.26 (d, J = 16.0 Hz, 1H), 2.43 (d, J = 13.2 Hz, 1H), 2.42 (s, 3H), (m, 3H), 1.66 (d, J = 16.4 Hz, 1H), 1.40 (d, J = 12.8 Hz, 1H), 1.11 (d, J = 12.8 Hz, 1H), 0.96 (s, 3H), 0.94 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ): 158.6, 143.4, 133.4, 129.6, 127.6, 56.7, 56.0, 46.6, 41.9, 34.9, 32.8, 32.5, 26.97, 26.95, IR: v 3302, 2923, 1461, 1455, 1335, 1286, 1164, 1090, 982, 785 cm -1 ; HRMS calcd. for C 17 H 24 N 2 O 3 S + [M+H] + : Found: Phosphorus pentachloride (12 mg, 0.05 mmol) was added in one portion to a solution of 2a-i (17 mg, 0.05 mmol) in THF (1 ml). The reaction mixture was heated to reflux for 1.5h. The reaction was quenched with sat. NH 4 Cl solution (10 ml). The aqueous phase was extracted with EtOAc (2 10 ml) and the combined organic extracts were washed with brine (10 ml), dried over NaSO 4, filtered, and concentrated under reduced pressure to give a colorless residue. The residue was purified by column chromatography to give 7.1 mg (47%) of 8 as a white solid. R f = 0.4 (EtOAc only). 1 H NMR (400 MHz, CDCl 3 ): 7.63 (d, J = 8.0 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H), 6.16 (brs, 1H), (m, 2H), 3.51 (d, J = 12.0 Hz, 1H), 2.99 (d, J = 14.0 Hz, 1H), 2.91 (dd, J = 15.2, 6.0 Hz, 1H), 2.44 (s, 3H), 2.17 (d, J = 14.0 Hz, 1H), 2.03 (d, J = 11.6 Hz, 1H), 1.98 (d, J = 10.8 Hz, 1H), 1.63 (d, J = 13.6 Hz, 1H), 1.01 (s, 3H), 0.89 (s, 3H), 0.84 (d, J = 13.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ): 174.9, 143.7, 133.5, 129.8, 127.4, 56.0, 54.3, 49.5, 46.7, 43.2, 33.1, 30.5, 28.4, 27.2, IR: v 3218, 2962, 2925, 1666, 1474, 1339, 1237, 1161, 1092, 989 cm -1 ; HRMS calcd. for C 17 H 24 N 2 NaO 3 S + [M+Na] + : Found: NATURE CHEMISTRY 20

21 Preliminary experiments on asymmetric catalysis Racemic 2b Enantiomeric Sample 2b NATURE CHEMISTRY 21

22 3. References 1. Clavier, H. & Nolan, S. P. Chem. Eur. J. 13, (2007). 2. Gioiello, A., Rosatelli, E., Teofrasti, M., Filipponi, P. & Pellicciari, R. ACS Comb. Sci. 15, (2013). 3. Krepski, L. R. & Hassner, A. J. Org. Chem. 43, (1978). 4. Okumoto, H., Ohtsuka, K. & Benjoya, S. Synlett. 20, (2007). 5. Margetić, D., Antonac, I. Z., Glasovac, Z., Eckert-Maksić, M. & Maksimović, L. Syn. Commun. 41, (2011). 6. Sharpless, K. B. & Hori, T. J. Org. Chem. 41, (1976). 7. Berlin, J. M. et al. Org. Lett. 9, (2007). 8. Cheng, B., Sunderhaus, J. D. & Martin, S. F. Org. Lett. 12, (2010). 9. Barile, F., Bassetti, M., D Annibale, A., Gerometta, R. & Palazzi, M. Eur. J. Org. Chem. 2011, (2011). 10. Senter, T. J., Fadeyi, O. O. & Lindsley, C. W. Org. Lett. 14, (2012). 11. Garzan, A. et al. Chem. Eur. J. 19, (2013). 12. Hollingworth, C. et al. Angew. Chem. Int. Ed. 50, (2011). 13. Xu, J., Fu, Y., Xiao, B., Gong, T. & Guo, Q. Tetrahedron Lett. 51, (2010). 14. Demnitz, F. W. J., Philippini, C. & Raphael, R. A. J. Org. Chem. 60, (1995). 15. Itooka, T., Matoba, K., Yamazaki, T., Muraoka, O. & Momose, T. Chem. Pharm. Bull. 34, (1986). NATURE CHEMISTRY 22

23 4. X-Ray data X-Ray data for 2a Crystal data and structure refinement for 2a (CCDC ). Empirical formula C17 H23 N O3 S Formula weight Temperature 153(2) K Wavelength Å Crystal system Orthorhombic Space group Pbca Unit cell dimensions a = (3) Å = 90. b = (4) Å = 90. c = (11) Å = 90. Volume (9) Å 3 Z 8 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1376 Crystal size 0.64 x 0.16 x 0.05 mm Theta range for data collection 3.17 to Index ranges -29<=h<=29, -26<=k<=26, -9<=l<=8 Reflections collected Independent reflections 3738 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.00 and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3738 / 0 / 203 NATURE CHEMISTRY 23

24 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Extinction coefficient 6.6(9)x10-6 Largest diff. peak and hole and e.å -3 X-Ray data for 2f Crystal data and structure refinement for 2f (CCDC ). Empirical formula C16 H21 N O3 S Formula weight Temperature 153(2) K Wavelength Å Crystal system Orthorhombic Space group Pbca Unit cell dimensions a = (6) Å = 90. b = (3) Å = 90. c = (8) Å = 90. Volume (2) Å 3 Z 8 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 1312 Crystal size 0.80 x 0.22 x 0.10 mm Theta range for data collection 3.43 to Index ranges -20<=h<=23, -9<=k<=9, -29<=l<=29 Reflections collected Independent reflections 3583 [R(int) = ] NATURE CHEMISTRY 24

25 Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.00 and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3583 / 0 / 192 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.å -3 X-Ray data for 2i Crystal data and structure refinement for 2i (CCDC ). Empirical formula C23 H27 N O4 S Formula weight Temperature 163(2) K Wavelength Å Crystal system Triclinic Space group P-1 Unit cell dimensions a = 7.253(4) Å = (9). b = (6) Å = (5). c = (8) Å = (9). Volume (10) Å 3 Z 2 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 440 Crystal size 0.40 x 0.22 x 0.14 mm Theta range for data collection 3.01 to NATURE CHEMISTRY 25

26 Index ranges Reflections collected <=h<=9, -13<=k<=13, -17<=l<=17 Independent reflections 4687 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.00 and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 4687 / 0 / 265 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.å -3 X-Ray data for 2n Crystal data and structure refinement for 2n (CCDC ). Empirical formula C15 H19 N O3 S Formula weight Temperature 153(2) K Wavelength Å Crystal system Monoclinic Space group P21/c Unit cell dimensions a = (12) Å = 90. b = (3) Å = (3). c = (6) Å = 90. Volume (13) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 NATURE CHEMISTRY 26

27 F(000) 624 Crystal size 0.65 x 0.24 x 0.10 mm Theta range for data collection 1.05 to Index ranges -26<=h<=26, -7<=k<=7, -15<=l<=15 Reflections collected Independent reflections 3310 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.00 and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3310 / 0 / 183 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.å -3 X-Ray data for 2q-i Crystal data and structure refinement for 2q-i (CCDC ). Empirical formula C25 H29 N5 O6 S Formula weight Temperature 153(2) K Wavelength Å Crystal system monoclinic Space group C 2/c Unit cell dimensions a = (2) Å = 90. b = (6) Å = (3). c = (2) Å = 90. Volume (7) Å3 Z 8 NATURE CHEMISTRY 27

28 Density (calculated) Mg/m3 Absorption coefficient mm-1 F(000) 2224 Crystal size x x mm Theta range for data collection to Index ranges -33<=h<=35, -11<=k<=11, -30<=l<=30 Reflections collected Independent reflections 5735 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.00 and Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 5735 / 13 / 359 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Extinction coefficient n/a Largest diff. peak and hole and e.å-3 X-Ray data for 2q-ii Crystal data and structure refinement for 2q-ii (CCDC ). Empirical formula C25 H29 N5 O6 S Formula weight Temperature 153(2) K Wavelength Å Crystal system orthorhombic Space group P Unit cell dimensions a = (4) Å = 90. NATURE CHEMISTRY 28

29 b = (9) Å = 90. c = (14) Å = 90. Volume (3) Å3 Z 4 Density (calculated) Mg/m3 Absorption coefficient mm-1 F(000) 1112 Crystal size 0.34 x 0.11 x 0.08 mm Theta range for data collection to Index ranges -9<=h<=9, -16<=k<=16, -28<=l<=28 Reflections collected Independent reflections 4388 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.00 and Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4388 / 0 / 340 Goodness-of-fit on F Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Absolute structure parameter 0.52(12) Extinction coefficient n/a Largest diff. peak and hole and e.å-3 Note that: the close H...H contacts are a consequence of the molecular conformation. X-Ray data for 8 Crystal data and structure refinement for 8 (CCDC ). Empirical formula C17 H24 N2 O3 S NATURE CHEMISTRY 29

30 Formula weight Temperature 153(2) K Wavelength Å Crystal system Monoclinic Space group C2/c Unit cell dimensions a = (3) Å = 90. b = (4) Å = (8). c = (9) Å = 90. Volume (4) Å3 Z 8 Density (calculated) Mg/m3 Absorption coefficient mm-1 F(000) 1440 Crystal size 0.55 x 0.35 x 0.12 mm Theta range for data collection 1.02 to Index ranges -50<=h<=50, -7<=k<=7, -18<=l<=18 Reflections collected Independent reflections 3557 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.00 and Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 3557 / 90 / 233 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.å-3 NATURE CHEMISTRY 30

31 X-Ray data for enamine derivative 2o-i Crystal data and structure refinement for enamine derivative 2o-i (CCDC ). Empirical formula C23 H32 N2 O4 Formula weight Temperature 298(2) K Wavelength Å Crystal system monoclinic Space group P 21/c Unit cell dimensions a = (4) Å = 90. b = (3) Å = (5). c = (4) Å = 90. Volume (9) Å 3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient mm -1 F(000) 864 Crystal size x x mm Theta range for data collection to Index ranges -17<=h<=16, -12<=k<=12, -17<=l<=17 Reflections collected Independent reflections 3919 [R(int) = ] Completeness to theta = % Absorption correction Semi-empirical from equivalents Max. and min. transmission 1.00 and Refinement method Full-matrix least-squares on F 2 Data / restraints / parameters 3919 / 61 / 292 Goodness-of-fit on F NATURE CHEMISTRY 31

32 Final R indices [I>2sigma(I)] R1 = , wr2 = R indices (all data) R1 = , wr2 = Extinction coefficient n/a Largest diff. peak and hole and e.å -3 X-Ray data for Rh[P(C 6 H 3 (CF 3 ) 2 ) 3 ] 2 COCl Note: because the Rh ion sits on a crystallographic inversion center, we report a weighted average of the structure of the individual complexes arranged in the crystal. Crystal data and structure refinement for Rh[P(C 6 H 3 (CF 3 ) 2 ) 3 ] 2 COCl (CCDC ). Empirical formula C49 H18 Cl F36 O P2 Rh Formula weight Temperature 100(2) K Wavelength Å Crystal system triclinic Space group P -1 Unit cell dimensions a = (3) Å = (6). b = (4) Å = (6). c = (4) Å = (6). Volume (7) Å3 Z 1 Density (calculated) Mg/m3 Absorption coefficient mm-1 F(000) 736 Crystal size x x mm Theta range for data collection to Index ranges -13<=h<=13, -15<=k<=15, -15<=l<=14 Reflections collected Independent reflections 6183 [R(int) = ] NATURE CHEMISTRY 32

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