Supporting Information

Supporting Information Wiley-VCH 2007 69451 Weinheim, Germany

Supporting Information for Catalytic Enantioselective Conjugate Reduction of β,β- Disubstituted α,β-unsaturated sulfones Tomás Llamas, Ramón Gómez Arrayás, and Juan C. Carretero* Departamento de Química Orgánica. Facultad de Ciencias. Universidad Autónoma de Madrid. Cantoblanco. 28049 Madrid. Spain. Table of Contents 1. EXPERIMENTAL SECTION.. S 2 - General Methods... S 2 - Synthesis of methyl 2-pyridyl sulfone... S 2 - Typical procedure for the synthesis of b,b-disubstituted a,b-unsaturated sulfones... S 3 - Typical procedure for the asymmetric conjugate reduction... S 6 - Protocols for functionalization/desulfonylation... S 10 2. NMR SPECTRA OF NEW COMPOUNDS... S 14 S 1

1. EXPERIMENTAL SECTION General methods All the reactions were carried out in anhydrous solvents and under argon atmosphere. Melting points were taken in open-end capillary tubes. NMR spectra were recorded at 300 MHz ( 1 H), 75 MHz ( 13 C), at room temperature in CDCl 3 [calibrated at 7.26 ppm ( 1 H), and 77.0 ppm ( 13 C)]. Mass spectra (MS) were determined under electospray ionization (ESI). HPLC experiments were conducted using a Chiralpak IA column. Flash column chromatography was performed using silica gel Merk-60 (230-400 mesh). Below are the structures of the chiral ligands considered in the screening test to optimize the enantioselectivity of the conjugate reduction. (R)-Binap t-bu O OMe O Ph 2 P PPh 2 O P t-bu 2 O PPh 2 PCy 2 PPh 2 Fe PPh 2 NMe O P t-bu O PPh 2 2 Fe PPh 2 O OMe t-bu (R)-DTBM-Segphos 2 O (R)-Segphos (R,S)-Josiphos Taniaphos Synthesis of methyl 2-pyridyl sulfone DBU (1.1 eq.) MeI (1.1 eq.) N SH THF:CH 3 CN N SMe 0 ºC 25 ºC H 2 O 2 (3 eq.) Na 2 WO 4 2H 2 O (10 mol%) AcOEt:H 2 O (10:1) I, 92% 99% N SO 2 Me To a solution of 2-mercaptopyridine (5.0 g, 45 mmol) in THF (90 ml) and CH 3 CN (9 ml), 1 cooled to 0 ºC, was added DBU (6.6 ml, 49.5 mmol). The resulting mixture was stirred at 0 ºC for 5 min before MeI (3.1 ml, 49.5 mmol) was slowly added. Then, the ice bath was removed and the mixture was stirred for 4 h. The reaction mixture was washed with water (40 ml) and the aqueous layer was extracted with EtOAc (2 x 40 ml). The combined organic layers were dried (MgSO 4 ), filtered and concentrated. The residue was purified by flash chromatography (n-hexane-etoac 2:1) to afford the methyl 2-pyridyl sulfide (I) as a colourless oil; yield: 5.20 g (92%). 1 H NMR (300 MHz): d 8.42 (m, 1H), 7.47 (m, 1H), 7.16 (m, 1H), 6.96 (m, 1H), 2.55 (s, 3H). 13 C NMR (75 MHz): d 159.9, 149.3, 135.6, 121.3, 119.0, 13.1. 1 CH 3 CN was added to improve solubility of the sulfone S 2

To a solution of I (5.0 g, 39.9 mmol) in EtOAc (50 ml) was added H 2 O (6 ml) and Na 2 WO 4 2H 2 O (1.3 g, 4.0 mmol). The resulting mixture was cooled to 0 ºC before a 30% solution of H 2 O 2 (12.9 ml, 120 mmol) was added dropwise. The reaction was stirred at 0 ºC for 30 min and at rt for 1 h. Then it was cooled to 0 ºC and aqueous saturated NaHSO 3 (10 ml) was added slowly. The organic layer was separated and the aqueous layer was extracted with EtOAc (2 x 20 ml). The combined organic layers were dried (MgSO 4 ), filtered and concentrated. The residue was purified by flash chromathograpy (n-hexane-etoac 2:1) to afford the sulfone as a colourless oil; yield: 6.3 g (99%). 1 H NMR (300 MHz): d 8.77-8.70 (m, 1H), 8.12-7.89 (m, 2H), 7.62-7.49 (m, 1H), 3.21 (s, 3H). 13 C NMR (75 MHz): d 157.8, 149.9, 138.3, 127.4, 121.0, 39.9. Typical procedure for the synthesis of b,b-disubstituted a,b-unsaturated sulfones: (E)-2-Phenyl-1-phenylsulfonyl-1-propene (1). To a solution of 3.2 mmol of methyl phenyl sulfone (0.5 g) in THF (20 ml), cooled to - 78 ºC, was added a 2.5 M solution of n-buli in hexane (1.4 ml, 3.5 mmol). The mixture was stirred at -78 ºC for 30 min before acetophenone (388 µl, 3.5 mmol) was added. The resulting orange solution was stirred at -78 ºC for 90 min, and then it was treated with aqueous saturated NH 4 Cl (10 ml). The organic layer was separated and the aqueous layer was extracted with EtOAc (2 x 20 ml). The combined organic layers were dried (MgSO 4 ), filtered and concentrated. The crude resulting alcohol and DMAP (40 mg, 0.3 mmol) were dissolved in CH 2 Cl 2 (15 ml). The mixture was cooled to 0 ºC before Et 3 N (892 µl, 6.4 mmol) and TFAA (534 µl, 3.8 mmol) were successively added. The reaction mixture was stirred at 0 ºC for 30 min, allowed to reach rt and stirred at rt overnight. After hydrolysis with aqueous saturated NH 4 Cl (10 ml). The organic layer was separated and the aqueous layer was extracted with CH 2 Cl 2. The combined organic layers were dried (MgSO 4 ), filtered and concentrated. The residue was purified by flash chromatography (n-hexane-etoac 2:1) to afford the sulfone as a white solid; yield: 0.58 g (70%); mp = 78-79 ºC. 1 H NMR (300 MHz): d 8.00-7.98 (m, 1H), 7.98-7.95 (m, 1H), 7.66-7.52 (m, 3H), 7.40-7.35 (m, 5H), 6.61 (q, J= 1.1 Hz, 1H), 2.54 (d, J= 1.1 Hz, 3H). 13 C NMR (75 MHz): d?153.4, 142.1, 140.0, 133.1, 129.8, 129.1, 128.6, 127.3, 127.1, 126.2, 17.1. (E)-2-Phenyl-1-[(2-pyridyl)sulfonyl)]-1-propene (2a). White solid; mp = 82-83 ºC; yield: 0.52 g (63%). 1 H NMR (300 MHz): d 8.74 (ddd, J= 0.9, 1.7, 7.7 Hz, 1H), 8.17 (dt, J= 0.9, 7.7 Hz, 1H), 8.01 (dt, J= 1.7, 7.7 Hz, 1H), 7.57 (ddd, J= 1.0, 4.6, 7.8 Hz, S 3

1H), 7.52-7.28 (m, 5H), 6.74 (q, J= 1.0 Hz, 1H), 2.57 (d, J= 1.0 Hz, 3H). 13 C NMR (75 MHz): d?159.4, 155.0, 140.0, 138.0, 130.0, 128.7, 127.0, 126.3, 124.8, 121.7, 17.6. HRMS (FAB+) Calcd for C 14 H 14 NO 2 S, 260.0745; found, 260.0748. (E)-2-(p-Methoxyphenyl)-1-[(2-pyridyl)sulfonyl)]-1-propene (2b). Yellow solid; mp = 81-82 ºC; yield: 0.64 g (69%). 1 H NMR (300 MHz): d 8.76-8.72 (m, 1H), 8.18-8.13 (m, 1H), 7.95 (dt, J= 1.7, 7.7 Hz, 1H), 7.57 (ddd, J= 1.1, 4.5, 7.7 Hz, 1H), 7.43 (d, J= 9.0, 2H), 6.88 (d, J= 9.0, 2H), 6.72 (q, J= 1.0 Hz, 1H), 3.58 (s, 3H), 2.57 (d, J= 1.0 Hz, 3H). 13 C NMR (75 MHz): δ 161.2, 159.7, 155.3, 150.2, 137.9, 131.9, 127.9, 126.8, 122.8, 121.6, 114.0, 55.3, 17.3. (E)-2-(p-Nitrophenyl)-1-[(2-pyridyl)sulfonyl)]-1-propene (2c). Yellow solid; mp = 120-121 ºC; yield: 0.65 g (66%). 1 H NMR (300 MHz): δ 8.76-8.73 (m, 1H), 8.22 (d, J= 8.9 Hz, 2H), 8.18-8.14 (m, 1H), 7.99 (dt, J= 1.7, 7.7 Hz, 1H), 7.61-7.53 (m, 3H), 6.83 (q, J= 1.2 Hz, 1H), 2.61 (d, J= 1.2 Hz, 3H). 13 C NMR (75 MHz): δ 158.9, 153.2, 150.3, 148.4, 146.4, 138.2, 127.8, 127.4, 127.3, 123.9, 121.8, 17.8. (E)-2-(p-Bromophenyl-1-[(2-pyridyl)sulfonyl)]-1-propene (2d). Yellow solid; mp = 94-95 ºC; yield: 0.66 g (61%). 1 H NMR (300 MHz): d 8.77-8.73 (m, 1H), 8.18-8.13 (m, 1H), 7.97 (dt, J= 1.7, 7.7 Hz, 1H), 7.57-7.47 (m, 3H), 7.31 (d, J= 8.7, 2H), 6.76 (q, J= 1.0 Hz, 1H), 2.57 (d, J= 1.0 Hz, 3H). 13 C NMR (75 MHz): δ 159.3, 154.5, 150.3, 138.9, 138.1, 131.9, 127.9, 127.1, 125.3, 124.4, 121.7, 17.5. (E)-2-[(p-Trifluoromethyl)phenyl]-1-[(2-pyridyl)sulfonyl)]-1-propene (2e). White solid; mp = 63-64 ºC; yield: 0.42 g (51%). 1 H NMR (300 MHz): δ?8.75 (ddd, J= 0.9, 1.7, 4.7 Hz, 1H), 8.17 (dt, J= 1.0, 7.9 Hz, 1H), 7.98 (dt, J= 1.7, 7.8 Hz, 1H), 7.67-7.52 (m, 2H), 7.58-7.52 (m, 3H), 6.80 (q, J= 1.2 Hz, 1H), 2.61 (d, J= 1.2 Hz, 3H). 13 C NMR (75 MHz): δ?159.0, 154.2, 150.3, 143.7, 138.2, 131.5 (q, J C-F = 32.5 Hz), 127.2, 126.8, 126.7, 125.6 (q, J C-F = 3.9 Hz), 121.7, 17.6. (E)-2-(o-Methylphenyl)-1-[(2-pyridyl)sulfonyl)]-1-propene (2f). White solid; mp = 74-75 ºC; yield: 0.39 g (44%). 1 H NMR (300 MHz): δ 8.73 (ddd, J= 0.9, 1.7, 4.7 Hz, 1H), 8.13 (dt, J= 0.9, 7.8 Hz, 1H), 7.96 (dt, J= 1.7 y 7.7 Hz, 1H), 7.53 (ddd, J= 1.4, 4.6, 7.7 Hz, 1H), 7.21-7.10 (m, 3H), 7.05-7.00 (m, 1H), 6.38 (q, J= 1.3 Hz, 1H), 2.45 (d, J= 1.3 Hz, 3H), 2.21 (s, 3H). 13 C NMR (75 MHz): δ 159.3, 158.4, 150.1, 141.5, 138.0, 133.6, 130.5, 128.3, 127.0, 126.8, 126.5, 125.7, 121.4, 20.2, 19.3. S 4

(E)-2-(o-Bromophenyl-1-[(2-pyridyl)sulfonyl)]-1-propene (2g). White solid; mp = 126-127 ºC; yield: 0.48 g (45%). 1 H NMR (300 MHz): δ 8.89-8.77 (m, 1H), 8.20-8.15 (m, 1H), 7.99 (dt, J= 1.8, 7.7 Hz, 1H), 7.69-7.53 (m, 2H), 7.35-7.27 (m, 1H), 7.24-7.16 (m, 2H), 6.49 (q, J= 1.3 Hz, 1H), 2.54 (d, J= 1.3 Hz, 3H). 13 C NMR (75 MHz): δ 159.1, 157.1, 150.3, 142.6, 138.0, 133.1, 129.8, 128.5, 128.3, 127.5, 127.1, 121.8, 120.2, 20.0. (E)-2-(2-Naphtyl)-1-[(2-pyridyl)sulfonyl)]-1-propene (2h). White solid; mp = 127-128 ºC; yield: 0.58 g (59%). 1 H NMR (300 MHz): δ 8.80-8.74 (m, 1H), 8.22-8.16 (m, 1H), 8.01-7.94 (m, 2H), 7.89-7.80 (m, 3H), 7.57-7.49 (m, 4H), 6.91 (q, J= 1.2 Hz, 1H), 2.70 (d, J= 1.2 Hz, 3H). 13 C NMR (75 MHz): δ 159.5, 155.7, 150.3, 138.1, 137.1, 133.8, 132.9, 128.6, 128.4, 127.5, 127.2, 127.0, 126.7, 126.4, 125.1, 123.4, 121.7, 17.6. (E)- and (Z)-2-Phenyl-1-[(2-pyridyl)sulfonyl)]-1-butene [(E)-4 and (Z)-4). Purification of the crude mixture by flash chromatography (n-hexane-etoac 2:1) provided (E)-4 (0.26 g, 29%), followed by (Z)-4 (0.24 g, 27%), both as yellow oils. (E)- 4: 1 H NMR (300 MHz): δ 8.76-8.72 (m, 1H), 8.18-8.14 (m, 1H), 7.96 (dt, J= 1.6, 7.8 Hz, 1H), 7.55-7.49 (m, 1H), 7.40-7.36 (m, 5H), 6.64 (s, 1H), 3.11 (q, J= 7.7 Hz, 2H), 0.99 (t, J= 7.7 Hz, 3H). 13 C NMR (75 MHz): δ 162.1, 159.4, 150.2, 138.7, 138.0, 129.7, 128.6, 126.9, 126.7, 124.5, 121.6, 24.0, 13.1. (Z)-4: 1 H NMR (300 MHz): δ 8.67-8.64 (m, 1H), 7.60 (dt, J= 1.7, 7.7 Hz, 1H), 7.45 (d, J= 7.7 Hz, 1H), 7.38-7.32 (m, 1H), 7.23-7.13 (m, 3H), 6.99-6.94 (m, 2H), 6.71 (t, J= 1.3 Hz, 1H), 2.46 (dq, J= 1.3, 7.5 Hz, 2H), 1.06 (t, J= 7.5 Hz, 3H). 13 C NMR (75 MHz): δ 161.2, 158.4, 149.6, 137.2, 136.7, 127.9, 127.5, 127.2, 126.4, 125.7, 122.0, 33.7, 11.3. (E)- and (Z)-2-Methyl-1-[(2-pyridyl)sulfonyl)]-3-tetrahydropyranoxy-1-propene [(E)-5 and (Z)-5]. Purification of the crude mixture by flash chromatography (nhexane-etoac 2:1) provided (E)-5 (0.21 g, 22%), followed by (Z)-5 (0.25 g, 26%), both as colorless oils. (E)-5: 1 H NMR (300 MHz): δ 8.70 (d, J= 4.6 Hz, 1H), 8.06 (d, J= 7.9 Hz, 1H), 7.92 (dt, J= 1.7, 7.7 Hz, 1H), 7.49 (ddd, J= 1.0, 4.7, 7.8 Hz, 1H), 6.35 (q, J= 1.4 Hz, 1H), 4.72 (q, J= 6.9 Hz, 2H), 4.56 (t, J= 3.6 Hz, 1H) 3.82-3.72 (m, 1H), 3.48-3.40 (m, 1H), 2.02 (d, J= 0.9 Hz, 3H), 1.85-1.45 (m, 6H). 13 C NMR (75 MHz): δ 159.1, 157.8, 150.2, 138.5, 138.0, 127.0, 124.0, 121.6, 98.8, 65.0, 62.4, 30.4, 25.2, 22.1, 19.4. (Z)-5: 1 H NMR (300 MHz): δ 8.73 (ddd, J= 0.9, 1.6, 4.7 Hz, 1H), 8.11 (dt, J= 1.0, 7.9 Hz, 1H), 7.93 (dt, J= 1.7, 7.7 Hz, 1H), 7.51 (ddd, J= 1.2, 4.7, 7.6 Hz, 1H), 6.65 (q, J= 1.4 Hz, 1H), 4.62 (t, J= 3.1 Hz, 1H), 4.25 (dd, J= 1.6, 16.6 Hz, 1H), 3.96 (dd, J= S 5

1.6, 16.6 Hz, 1H), 3.82-3.72 (m, 1H), 3.55-3.45 (m, 1H), 2.14 (d, J= 1.2 Hz, 3H), 1.85-1.45 (m, 6H). 13 C NMR (75 MHz): δ 159.3, 155.9, 150.2, 137.9, 126.9, 122.1, 121.6, 98.1, 69.7, 62.0, 30.1, 25.1, 18.9, 15.1. (E)-2,3,3-Trimethyl-1-[(2-pyridyl)sulfonyl)]-1-butene (6). Yellow oil; yield: 0.46 g (60%). 1 H NMR (300 MHz): δ 8.73-8.70 (m, 1H), 8.12-8.08 (m, 1H), 7.93 (dt, J= 1.7, 7.7 Hz, 1H), 7.50 (ddd, J= 1.2, 4.7, 7.8, 1H), 6.40 (d, J= 1.0 Hz, 1H), 2.15 (d, J= 1.0 Hz, 3H), 1.09 (s, 9H). 13 C NMR (75 MHz): δ 167.4, 159.3, 149.9, 137.8, 126.7, 122.1, 121.4, 38.4, 27.9, 14.4. (E)-4-[(2-Pyridyl)sulfonylmethylene]chroman (7). White solid; mp = 138-139ºC; yield: 0.69 g (75%). 1 H NMR (300 MHz): δ 8.71 (ddd, J= 0.9, 1.7, 4.7 Hz, 1H), 8.12 (dt, J= 1.1, 7.9 Hz, 1H), 7.94 (dt, J= 1.6, 7.7 Hz, 1H), 7.53-7.47 (m, 2H), 7.32-7.27 (m, 1H), 6.94-6.85 (m, 3H), 4.26 (t, J= 5.9 Hz, 2H), 3.46-3.41 (m, 2H). 13 C NMR (75 MHz): δ 159.6, 156.9, 150.3, 148.7, 138.1, 132.9, 127.0, 125.1, 121.5, 121.1, 118.9, 118.3, 117.8, 65.2, 26.2. (E)-1-[(2-Pyridyl)sulfonylmethylene]indan (8). White solid; mp = 88-89 ºC; yield: 0.63 (73%). 1 H NMR (300 MHz): δ 8.72 (d, J= 4.5 Hz, 1H), 8.15 (d, J= 8.0 Hz, 1H), 7.94 (dt, J= 1.7, 7.9 Hz, 1H), 7.57-7.47 (m, 2H), 7.43-7.33 (m, 2H), 7.30-7.22 (m, 1H), 6.85 (t, J= 2.5 Hz, 1H), 3.45-3.37 (m, 2H), 3.10 (t, J= 6.2 Hz, 2H). 13 C NMR (75 MHz): δ 162.8, 159.6, 150.2, 149.6, 138.3, 137.9, 132.0, 127.0, 126.8, 125.6, 122.2, 121.5, 114.6, 30.4, 29.7. Typical procedure for the asymmetric conjugate reduction of a,b-unsaturated sulfones: (S)-2-phenyl-1-[(2-pyridyl)sulfonyl)]propane (3a). A solution of CuCl (1.0 mg, 0.01 mmol), tbuona (1.0 mg, 0.01 mmol), (R)-Binap (6.2 mg, 0.01 mmol), PhSiH 3 (100 µl, 0.8 mmol) and (E)-2a (51.8 mg, 0.2 mmol) in toluene (1 ml, 0.2 M) was stirred at room temperature for 24 h. Aqueous saturated NH 4 Cl (20 µl) was added before the mixture was filtered through a short pad of Celite with a thin layer of anhydrous MgSO 4 on the top, and the filtrate was concentrated. The residue was purified by flash cromathography (n-hexane-etoac 4:1) to afford sulfone 3a as a white solid; yield: 49.5 mg (95%); mp = 71-72 ºC. Analysis by HPLC with chiral stationary phase (Daicel Chiralpak IA, i-proh-hexane 10/90, 0.6 ml/min, t R : 30.3 min for (R)- 20 isomer and 33.3 min for (S)-isomer, 210 nm) showed 94% ee ([α] D = +6 (c 1, CHCl 3 )). 1 H NMR (300 MHz): δ 8.63 (d, J= 4.7 Hz, 1H), 7.84 (d, J= 7.8 Hz, 1H), 7.78 S 6

(dt, J= 1.7, 7.7 Hz, 1H), 7.42 (ddd, J= 1.4, 4.7, 7.8 Hz, 1H), 7.19-7.05 (m, 5H), 3.89 (dd, J= 6.2, 13.9 Hz, 1H), 3.58-3.40 (m, 2H), 1.42 (d, J= 6.7 Hz, 3H). 13 C NMR (75 MHz): δ 157.5, 149.9, 143.3, 137.8, 128.4, 127.0. 126.9, 126.7, 122.0, 58.7, 35.0, 22.1. HRMS (FAB+) Calcd for C 14 H 16 NO 2 S, 262.0901; found, 262.0903. (S)-2-(p-Methoxyphenyl)-1-[(2-pyridyl)sulfonyl)]propane (3b). Colorless oil; yield: 92%. [α] 20 D = +7.5 (c 1, CHCl 3 ), 91% ee. HPLC: Daicel Chiralpak IA, i-proh-hexane 10/90, 0.6 ml/min, t R : 35.0 min (R)-isomer and 38.8 min (S)-isomer, 210 nm. 1 H NMR (300 MHz): δ 8.63 (ddd, J= 0.9, 1.5, 4.7 Hz, 1H), 7.85-7.74 (m, 2H), 7.42 (ddd, J= 1.6, 4.7, 7.1 Hz, 1H), 6.99 (d, J= 8.6 Hz, 2H), 6.67 (d, J= 8.6 Hz, 2H), 3.85 (dd, J= 6.8, 14.1 Hz, 1H), 3.73 (s, 3H), 3.55-3.36 (m, 2H), 1.39 (d, J= 6.9 Hz, 3H). 13 C NMR (75 MHz): δ 158.2, 157.6, 149.9, 137.7, 135.4, 127.9, 126.8, 122.0, 113.8, 58.9, 55.2, 34.2, 22.2. HRMS (FAB+) Calcd for C 15 H 18 NO 3 S, 291.0929; found, 291.0920. (S)-2-(p-Nitrophenyl)-1-[(2-pyridyl)sulfonyl)]propane (3c). White solid; yield: 93%; mp = 76-77 ºC. [α] 20 D = -4.9 (c 1.3, CHCl 3 ), 89% ee. HPLC: Daicel Chiralpak IA, i- PrOH-hexane 20/80, flow rate 0.6 ml/min, t R : 48.1 min (R)-isomer and 50.8 min (S)- isomer, 210 nm. 1 H NMR (300 MHz): δ 8.64 (ddd, J= 0.9, 1.4, 4.7 Hz, 1H), 8.03 (d, J= 8.8 Hz, 2H), 7.87 (dt, J= 1.4, 7.9 Hz, 1H), 7.82 (dt, J= 1.7 and 7.5 Hz, 1H), 7.46 (ddd, J= 1.5, 4.7, 7.4 Hz, 1H), 7.25 (d, J= 8.8 Hz, 2H), 3.96-3.85 (m, 1H), 3.69-3.56 (m, 2H), 1.46 (d, J= 6.8 Hz, 3H). 13 C NMR (75 MHz): δ 157.4, 150.7, 150.0, 146.8, 138.0, 128.0, 127.2, 123.7, 121.8, 57.8, 34.9, 22.0. HRMS (FAB+) Calcd for C 14 H 15 N 2 O 4 S, 307.0674; found, 307.0680. (S)-2-(p-Bromophenyl-1-[(2-pyridyl)sulfonyl)]propane (3d). Colorless oil; yield: 92%. [α] 20 D = +8.5 (c 1.25, CHCl 3 ), 92% ee. HPLC: Daicel Chiralpak IA, i-prohhexane 10/90, 0.6 ml/min, t R : 32.2 min (R)-isomer and 36.8 min (S)-isomer, 210 nm. 1 H NMR (300 MHz): δ 8.64-8.60 (m, 1H), 7.81-7.77 (m, 2H), 7.48-7.42 (m, 1H), 7.24 (d, J= 8.4 Hz, 2H), 6.95 (d, J= 8.4 Hz, 2H), 3.89 (dd, J= 7.5, 14.2 Hz, 1H), 3.56-3.38 (m, 2H), 1.40 (d, J= 6.8 Hz, 3H). 13 C NMR (75 MHz): δ 157.3, 149.9, 142.1, 137.8, 131.4, 128.8, 126.8, 121.9, 120.5, 58.4, 34.6, 22.0. HRMS (FAB+) Calcd for C 14 H 15 BrNO 3 S, 339.9929; found, 339.9925. (S)-1-[(2-Pyridyl)sulfonyl)]-2-[(p-trifluoromethyl)phenyl]propane (3e). Colorless oil; yield: 95%. [α] 20 D = +6.9 (c 1.9, CHCl 3 ), 92% ee. HPLC: Daicel Chiralpak IA, i- PrOH-hexane 10/90, 0.6 ml/min, t R : 27.6 min (R)-isomer and 30.5 min (S)-isomer, 210 nm. 1 H NMR (300 MHz): δ 8.61-8.57 (m, 1H), 7.76-7.72 (m, 2H), 7.43-7.34 (m, 3H), S 7

7.17 (d, J= 8.1 Hz, 2H), 3.96 (dd, J= 9.8, 16.3 Hz, 1H), 3.59-3.50 (m, 2H), 1.43 (d, J= 6.8 Hz, 3H). 13 C NMR (75 MHz): δ 157.3, 149.9, 147.0, 137.8, 129.0 (q, J C-F = 32.5 Hz), 127.5, 127.0, 125.3 (q, J C-F = 3.8 Hz), 121.9, 58.1, 35.1, 22.1. HRMS (FAB+) Calcd for C 15 H 15 F 3 NO 2 S, 330.0697; found, 330.0689. (S)-2-(o-Methylphenyl)-1-[(2-pyridyl)sulfonyl)]propane (3f). Colourless oil; yield: 93%. [α] 20 D = +21.3 (c 1, CHCl 3 ), 93% ee. HPLC: Daicel Chiralpak IA, i-prohhexane 10/90, 0.6 ml/min, t R : 23.9 min (R)-isomer and 25.8 min (S)-isomer, 210 nm. 1 H NMR (300 MHz): δ 8.64 (ddd, J= 0.9, 1.5, 4.7 Hz, 1H), 7.86-7.74 (m, 2H), 7.42 (ddd, J= 1.4, 4.7, 7.4 Hz, 1H), 7.00-6.95 (m, 4H), 3.85 (dd, J= 6.4, 14.0 Hz, 1H), 3.75 (sextet, J= 6.6 Hz, 1H), 3.54 (dd, J= 7.1, 14.0 Hz, 1H), 2.30 (s, 3H), 1.39 (d, J= 6.8 Hz, 3H). 13 C NMR (75 MHz): δ 157.6, 149.9, 141.6, 137.8, 135.1, 130.4, 126.9, 126.4, 126.2, 125.6, 121.8, 58.4, 29.8, 21.6, 19.3. HRMS (FAB+) Calcd for C 15 H 18 NO 2 S, 276.0980; found, 276.0982. (S)-2-(o-Bromophenyl-1-[(2-pyridyl)sulfonyl)]propane (3g). Colorless oil; yield: 90%. [α] 20 D = +25.4 (c 1.6, CHCl 3 ), 94% ee. HPLC: Daicel Chiralpak IA, i-prohhexane 10/90, 0.6 ml/min, t R : 29.9 min (R)-isomer and 33.0 min (S)-isomer, 210 nm. 1 H NMR (300 MHz): δ 8.65 (d, J= 4.6 Hz, 1H), 7.97 (d, J= 7.8 Hz, 1H), 7.84 (dt, J= 1.6, 7.8 Hz, 1H), 7.48-7.39 (m, 2H), 7.20-7.12 (m, 2H), 7.01-6.94 (m, 1H), 3.97-3.83 (m, 2H), 3.62-3.52 (m, 1H), 1.42 (d, J= 6.8 Hz, 3H). 13 C NMR (75 MHz): δ 157.2, 150.0, 142.2, 137.9, 133.0, 128.2, 127.8, 127.7, 127.1, 123.7, 122.1, 57.5, 33.7, 21.0. HRMS (FAB+) Calcd for C 14 H 15 BrNO 2 S, 339.9929; found, 339.9933. (S)-2-(2-Naphtyl)-1-[(2-pyridyl)sulfonyl)]propane (3h). White solid; yield: 89%; mp = 97-98 ºC. [α] 20 D = +13.2 (c 0.5, CHCl 3 ), 70% ee. HPLC: Daicel Chiralpak IA, i- PrOH-hexane 10/80, 0.6 ml/min, t R : 28.6 min (R)-isomer and 33.7 min (S)-isomer, 210 nm. 1 H NMR (300 MHz): δ 8.50 (ddd, J= 0.9, 1.6, 4.6 Hz, 1H), 7.73-7.65 (m, 3H), 7.59 (d, J= 8.5 Hz, 1H), 7.51-7.46 (m, 2H), 7.45-7.39 (m, 2H), 7.21-7.14 (m, 2H), 4.10-3.97 (m, 1H), 3.70-3.55 (m, 2H), 1.50 (d, J= 6.8 Hz, 3H). 13 C NMR (75 MHz): δ 157.3, 149.7, 140.3, 137.3, 133.1, 132.2, 128.2, 127.5, 127.4, 126.5, 126.0, 125.8, 125.6, 125.0, 121.9, 58.7, 35.3, 22.0. HRMS (FAB+) Calcd for C 18 H 18 NO 2 S, 312.0980; found, 312.0984. 20 (S)-2-Phenyl-1-[(2-pyridyl)sulfonyl)]butane [(S)-9]. Colorless oil; yield: 92%. [α] D = +20.3 (c 2, CHCl 3 ), 93% ee. HPLC: Daicel Chiralpak IA, i-proh-hexane 10/90, 0.6 ml/min, t R : 20.8 min (R)-isomer and 22.3 min (S)-isomer, 210 nm. 1 H NMR (300 S 8

MHz): δ 8.57 (d, J= 4.5 Hz, 1H), 7.72-7.68 (m, 2H), 7.39-7.32 (m, 1H), 7.10-7.04 (m, 3H), 7.00-6.95 (m, 2H), 3.94 (dd, J= 8.5, 14.6 Hz, 1H), 3.57 (dd, J= 5.6, 14.7 Hz, 1H), 3.23-3.11 (m, 1H), 1.93-1.80 (m, 1H), 1.71-1.58 (m, 1H), 0.76 (t, J= 7.4 Hz, 3H). 13 C NMR (75 MHz): δ 157.5, 149.8, 141.1, 137.6, 128.2, 127.8, 126.7, 126.6, 122.0, 57.5, 42.3, 29.4, 11.5. HRMS (FAB+) Calcd for C 15 H 18 NO 2 S, 276.0980; found, 276.0982. 20 (R)-2-Phenyl-1-[(2-pyridyl)sulfonyl)]butane [(R)-9]. Colorless oil; yield: 92%. [α] D = -19.6 (c 1.9, CHCl 3 ), 91% ee. HPLC: Daicel Chiralpak IA, i-proh-hexane 10/90, 0.6 ml/min, t R : 20.8 min (R)-isomer and 22.3 min (S)-isomer, 210 nm. 1 H NMR (300 MHz): δ 8.57 (d, J= 4.5 Hz, 1H), 7.72-7.68 (m, 2H), 7.39-7.32 (m, 1H), 7.10-7.04 (m, 3H), 7.00-6.95 (m, 2H), 3.94 (dd, J= 8.5, 14.6 Hz, 1H), 3.57 (dd, J= 5.6, 14.7 Hz, 1H), 3.23-3.11 (m, 1H), 1.93-1.80 (m, 1H), 1.71-1.58 (m, 1H), 0.76 (t, J= 7.4 Hz, 3H). 13 C NMR (75 MHz): δ 157.5, 149.8, 141.1, 137.6, 128.2, 127.8, 126.7, 126.6, 122.0, 57.5, 42.3, 29.4, 11.5. (2S)-2-Methyl-1-[(2-pyridyl)sulfonyl)]-3-tetrahydropyranoxypropane [(2S)-10]. Colorless oil; yield: 89%. [α] 20 D = +11.6 (c 1.4, CHCl 3 ), 91% ee. HPLC: Daicel Chiralpak IA, i-proh-hexane 10/90, 0.6 ml/min, t R : 30.1 and 34.4 min (2R)-isomers; 32.3 and 35.8 (2S)-isomers, 210 nm. 1 H NMR (300 MHz): δ 8.76 (d, J= 4.8 Hz, 1H), 8.11 (d, J= 7.9 Hz, 1H), 7.97 (dt, J= 1.6, 7.9 Hz, 1H), 7.55 (dd, J= 4.6, 7.6 Hz, 1H), 4.55-4.47 (m, 1H) 3.82-3.65 (m, 2H), 3.65-3.53 (m, 1H), 3.52-3.43 (m, 1H), 3.38 (dd, J= 4.8, 9.8 Hz, 1H), 3.32-3.20 (m, 1H), 2.47-2.32 (m, 1H), 1.85-1.42 (m, 6H), 1.12 (d, J= 6.7 Hz, 3H). 13 C NMR (75 MHz): δ 157.8, 150.1, 138.1, 127.2, 121.9, 98.9, 98.5, 71.1, 70.4, 62.1, 62.1, 55.0, 54.8, 30.4, 30.3, 29.2, 29.0, 25.3, 19.3, 19.2, 17.1, 17.0. (2R)-2-Methyl-1-[(2-pyridyl)sulfonyl)]-3-(tetrahydropyranoxy)propane [(2R)-10]. Colorless oil; yield: 91%. [α] 20 D = -12.0 (c 0.9, CHCl 3 ), 91% ee. HPLC: Daicel Chiralpak IA, i-proh-hexane 10/90, 0.6 ml/min, t R : 30.1 and 34.4 min [for the two (2R)-diastereoisomers]; 32.3 and 35.8 [for the two (2S)-diastereoisomers], 210 nm. 1 H NMR (300 MHz): δ 8.76 (d, J= 4.8 Hz, 1H), 8.11 (d, J= 7.9 Hz, 1H), 7.97 (dt, J= 1.6, 7.9 Hz, 1H), 7.55 (dd, J= 4.6, 7.6 Hz, 1H), 4.55-4.47 (m, 1H) 3.82-3.65 (m, 2H), 3.65-3.53 (m, 1H), 3.52-3.43 (m, 1H), 3.38 (dd, J= 4.8, 9.8 Hz, 1H), 3.32-3.20 (m, 1H), 2.47-2.32 (m, 1H), 1.85-1.42 (m, 6H), 1.12 (d, J= 6.7 Hz, 3H). 13 C NMR (75 MHz): δ 157.8, 150.1, 138.1, 127.2, 121.9, 98.9, 98.5, 71.1, 70.4, 62.1, 62.1, 55.0, 54.8, 30.4, 30.3, 29.2, 29.0, 25.3, 19.3, 19.2, 17.1, 17.0. S 9

(E)-1-[(2-Pyridyl)sulfonyl)]-2,3,3-(trimethyl)butane (11). Yellow oil; yield: 93%. [α] 20 D = +26.9 (c 2, CHCl 3 ), 91% ee. HPLC: Daicel Chiralpak IA, i-proh-hexane 10/90, 0.6 ml/min, t R : 16.6 min (R)-isomer and 18.8 min (S)-isomer, 210 nm. 1 H NMR (300 MHz): δ 8.75 (d, J= 4.2 Hz, 1H), 8.11 (d, J= 8.2 Hz, 1H), 7.96 (dt, J= 1.5, 7.8 Hz, 1H), 7.54 (dd, J= 5.0, 7.8 Hz, 1H), 3.62 (d, J= 13.9 Hz, 1H), 3.01 (dd, J= 10.0, 14.3 Hz, 1H), 1.94-1.82 (m, 1H), 1.07 (d, J= 6.9 Hz, 3H), 0.83 (s, 9H). 13 C NMR (75 MHz): δ. 157.7, 150.1, 138.0, 127.2, 122.1, 54.8, 37.6, 33.3, 26.8, 15.3. HRMS (FAB+) Calcd for C 12 H 20 NO 2 S, 242.1136; found, 242.1130. (S)-4-[(2-Pyridyl)sulfonylmethyl]chroman (12). Colorless oil; yield: 93%. [α] 20 D = - 19.6 (c 2, CHCl 3 ), 90% ee. HPLC: Daicel Chiralpak IA, i-proh-hexane 10/90, 0.6 ml/min, t R : 31.2 min (R)-isomer and 35.3 min (S)-isomer, 210 nm. 1 H NMR (300 MHz): δ 8.78 (d, J= 4.7 Hz, 1H), 8.15 (d, J= 7.8 Hz, 1H), 8.00 (dt, J= 1.5, 7.7 Hz, 1H), 7.58 (dd, J= 1.5, 7.7 Hz, 1H), 7.09 (d, J= 7.5 Hz, 2H), 6.89-6.75 (m, 2H), 4.29-4.10 (m, 2H), 3.89 (d, J= 11.8 Hz, 1H), 3.65-3.55 (m, 2H), 2.28 (d, J= 4.8 Hz, 2H). 13 C NMR (75 MHz): δ 157.7, 154.7, 150.2, 138.3, 128.9, 128.4, 127.5, 122.5, 121.9, 120.7, 117.3, 62.5, 57.1, 28.5, 26.7. HRMS (FAB+) Calcd for C 15 H 16 NO 3 S, 290.0773; found, 290.0780. (S)-1-[(2-Pyridyl)sulfonylmethyl]indan (13). Colorless oil; yield: 91%. [α] 20 D = +10.6 (c 1.9, CHCl 3 ), 90% ee. HPLC: Daicel Chiralpak IA, i-proh-hexane 10/90, flow rate 0.6 ml/min, t R : 34.1 min (R)-isomer and 37.4 min (S)-isomer, 210 nm. 1 H NMR (300 MHz): δ 8.77 (d, J= 4.9 Hz, 1H), 8.16 (d, J= 7.8 Hz, 1H), 7.99 (dt, J= 1.5, 7.6 Hz, 1H), 7.57 (dd, J= 4.6, 7.6 Hz, 1H), 7.25-7.15 (m, 4H), 3.97 (dd, J= 3.0, 14.0 Hz, 1H), 3.77-3.67 (m, 1H), 3.48 (dd, J= 10.2, 14.0 Hz, 1H), 3.00-2.80 (m, 2H), 2.50-2.37 (m, 1H), 2.05-1.90 (m, 1H). 13 C NMR (75 MHz): δ 157.6, 150.2, 143.6, 143.5, 138.2, 127.4, 127.2, 126.5, 124.7, 123.3, 122.0, 56.5, 38.9, 32.3, 31.3. Protocols for functionalization/desulfonylation (R)-1,3-Diphenylbutane (14). To a solution of sulfone 3a (50 mg, 0.19 mmol, 94% ee) in THF (5 ml), cooled to -78 ºC, was added a 2.5 M solution of n-buli in hexane (84 µl, 0.21 mmol). The resulting orange solution was stirred for 30 min at -78 ºC before it was added benzyl bromide (25 µl, 0.21 mmol). The mixture was stirred at -78 ºC for 2 h, and then aqueous saturated NH 4 Cl (10 ml) was added. The organic layer was S 10

separated and the aqueous layer was extracted with EtOAc (2 x 15 ml). The combined organic layers were dried (MgSO 4 ), filtered and concentrated. The residue was dissolved in MeOH (5 ml) and treated with 5 % Na(Hg) (230 mg) and Na 2 HPO 4 (93 mg, 0.6 mmol). The resulting suspension was stirred for 5 h at rt before it was poured into CH 2 Cl 2 (10 ml), filtered and washed with water (2 x 5 ml). The aqueous phase was extracted with CH 2 Cl 2 (3 x 5 ml) and the combined organic phase was dried (MgSO 4 ), filtered and concentrated. The residue was purified by flash chromatography (n-hexane-etoac 100:1), to afford 14 as a colorless oil; yield: 30 mg (75%). [α] 20 D = +9.2 (c 0.7, CHCl 3 ), 94% ee. 1 H NMR (300 MHz): δ 7.45-7.35 (m, 5H), 7.20-7.09 (m, 5H), 2.59 (sextuplet, J= 7.1 Hz, 1H), 2.48 (t, J= 7.9 Hz, 2H), 2.08-1.65 (m, 2H), 1.22 (d, J= 7.1 Hz, 3H). 13 C NMR (75 MHz): δ 139.7, 139.4. 128.7, 128.4, 128.3, 128.1 126.1, 125.8, 42.5, 41.4, 33.1, 21.2. HRMS (FAB+) Calcd for C 16 H 19, 211.1409; found, 211.1420. Ethyl (R)-3-phenylbutyrate (15). 2 To a solution of sulfone 3a (50 mg, 0.19 mmol, 94% ee) in THF (5 ml), cooled to -78 ºC, was added a 2.5 M solution of n-buli in hexane (84 µl, 0.21 mmol). The resulting orange solution was stirred at -78 ºC for 30 min before ethyl chloroformate (21 µl, 0.21 mmol) was added. The mixture was stirred at -78 ºC for 2 h, and then saturated aqueous NH 4 Cl (10 ml) was added. The organic phase was separated and the aqueous layer was extracted with EtOAc (2 x 10 ml). The combined organic phase was dried (MgSO 4 ), filtered and concentrated. The residue was dissolved in THF (2 ml) and added to a suspension of activated Zn (350 mg) in THF (4 ml) and aqueous saturated NH 4 Cl (4 ml). The mixture was stirred for 12 h at rt before it was filtered through Celite and washed with CH 2 Cl 2 (2 x 10 ml). The combined organic phase was dried (MgSO 4 ), filtered and concentrated. The residue was purified by flash chromatography (n-hexane-etoac 4:1) to afford 15 as a colorless oil; yield: 29.4 mg (80%). [α] 20 D = -17.9 (c 0.8, CHCl 3 ), 94% ee; [α] Lit D (for the (S)-isomer of 90% ee) = +19.0 (c 1.1, CHCl 3 ). 1 H NMR (300 MHz): δ 7.32-7.27 (m, 2H), 7.22-7.17 (m, 3H), 4.07 (q, J= 7.1 Hz, 2H), 3.28 (sextet, J= 7.6 Hz, 1H), 2.61 (dd, J= 7.0, 15.0 Hz, 1H), 2.53 (dd, J= 8.0, 15.0 Hz, 1H), 1.31 (d, J= 7.1 Hz, 3H), 1.18 (t, J= 7.1 Hz, 3H). 13 C NMR (75 MHz): δ 172.3, 145.7, 128.4, 126.7, 126.3, 60.2, 42.9, 36.5, 21.7, 14.1. 2 (S)-isomer: D. H. Appella, Y. Moritani, R. Shintani, E. M. Ferreira, S. L. Buchwald, J. Am. Chem. Soc. 1999, 121, 9473. S 11

(R)-1,3-Diphenylbutan-1-one (16). 3 To a solution of sulfone 3a (50 mg, 0.19 mmol, 94% ee) in THF (5 ml), cooled to -78 ºC, was added a 2.5 M solution of n-buli in hexane (84 µl, 0.21 mmol). The resulting orange solution was stirred for 30 min at -78 ºC before benzoyl chloride (24 µl, 0.21 mmol) was added. The resulting solution was stirred at -78 ºC for 2 h and then it was added aqueous saturated NH 4 Cl (10 ml). The organic phase was separated and the aqueous phase was extracted with EtOAc (2 x 10 ml). The combined organic phase was dried (MgSO 4 ), filtered and concentrated. The residue was dissolved in THF (2 ml) and added to a suspension of Zn activated (350 mg) in THF (4 ml) and aqueous saturated NH 4 Cl (4 ml). The mixture was stirred for 12 h at rt before it was filtered through Celite and washed with CH 2 Cl 2 (2 x 10 ml). The combined organic phase was dried (MgSO 4 ), filtered and concentrated. The residue was purified by flash chromatography (n-hexane-etoac 3:1), to afford 16 as a white solid; yield: 29.2 mg (69%); mp = 51-52 ºC. [α] 20 D = -16.2 (c 0.7, CHCl 3 ), 94% ee; [α] Lit D (for a sample of 82% ee) = -13.5 (c 1.0, CCl 4 ). HPLC: Daicel Chiralcel OD, i- PrOH-hexane 2/98, 1 ml/min, t R : 17.6 min (S)-isomer and 19.9 min (R)-isomer, 210 nm. 1 H NMR (300 MHz): δ 7.93 (dd, J= 0.9, 8.0 Hz, 2H), 7.57-7.52 (m, 1H), 7.44 (dt, J= 1.8, 8.2 Hz, 2H), 7.33-7.27 (m, 4H), 7.22-7.17 (m, 1H), 3.51 (sextet, J= 7.2 Hz, 1H), 3.31 (dd, J= 5.8, 16.5 Hz, 1H), 3.16 (dd, J= 8.1, 16.2 Hz, 1H), 1.34 (d, J= 6.8 Hz, 3H). 13 C NMR (75 MHz): δ 199.0, 146.5, 132.9, 128.5, 128.2, 128.0, 126.8, 126.2, 47.0, 35.5, 21.8. (1E,3R)-1,3-diphenyl-1-butene (17). 4 To a solution of sulfone 3a (46 mg, 0.18 mmol, 94% ee) in DME (5 ml), cooled to -78 ºC, was added a 0.5 M solution of KHMDS in toluene (0.72 ml, 0.36 mmol). The resulting orange solution was stirred at -78 ºC for 3 min before benzaldehyde (28 µl, 0.27 mmol) was added. The resulting solution was stirred at -78 ºC for 2 h, and then saturated aqueous NH 4 Cl (10 ml) was added. The organic phase was separated and the aqueous phase was extracted with EtOAc (2 x 10 ml). The combined organic phase was dried (MgSO 4 ), filtered and concentrated. The residue was purified by flash chromatography (n-hexane-etoac 100:1) to afford 17 as a colorless oil; yield: 32.5 mg (87%). [α] 20 D = +40.0 (c 0.8, CHCl 3 ), 94% ee; [α] Lit D (for a sample of 81% ee) = +32.0 (c 0.4, CHCl 3 ). HPLC: Daicel Chiralcel OD, i-proh- 3 Y. Kanazawa, Y. Tsuchiya, K. Kobayashi, T. Shiomi, J-i. Itho, M. Kikuchi, Y. Yamamoto, H. Nishiyama, Chem. Eur. J. 2006, 12, 63. 4 P. Mauleón; J. C. Carretero, Org. Lett. 2004, 6, 3195. S 12

hexane 0.5/99.5, flow rate 0.2 ml/min, t R : 28.4 min (S)-isomer and 30.9 min (R)- isomer, 210 nm. 1 H NMR (300 MHz): δ 7.41-7.20 (m, 10H), 6.44 (d, J= 4.6 Hz, 2H), 3.74-3.64 (m, 1H), 1.50 (d, J= 7.1 Hz, 3H). 13 C NMR (75 MHz): δ 145.6, 137.6, 135.2, 128.5, 128.4, 127.3, 127.0, 126.2, 126.1, 42.5, 21.2. HRMS (FAB+) Calcd for C 16 H 17, 209.1252; found, 209.1243. S 13

2. NMR SPECTRA OF NEW COM POUNDS Ph Me 1 SO 2 Ph S 14

Ph Me 2a SO 2 (2-Py) S 15

MeO Me SO 2 (2-Py) 2b S 16

O 2 N Me SO 2 (2-Py) 2c S 17

Br Me SO 2 (2-Py) 2d S 18

F 3 C Me SO 2 (2-Py) 2e S 19

Me SO 2 (2-Py) 2f S 20

Br Me 2g SO 2 (2-Py) S 21

Me SO 2 (2-Py) 2h S 22

Ph Et (E)-4 SO 2 (2-Py) S 23

Et Ph SO 2 (2-Py) (Z)-4 S 24

SO 2 (2-Py) O O (E)-5 S 25

SO 2 (2-Py) O O (Z)-5 S 26

SO 2 (2-Py) 6 S 27

SO 2 (2-Py) O 7 S 28

SO 2 (2-Py) 8 S 29

Ph Me SO 2 (2-Py) 3a S 30

MeO Me SO 2 (2-Py) 3b S 31

O 2 N Me SO 2 (2-Py) 3c S 32

Br Me SO 2 (2-Py) 3d S 33

F 3 C Me SO 2 (2-Py) 3e S 34

Me SO 2 (2-Py) 3f S 35

Br Me 3g SO 2 (2-Py) S 36

Me 3h SO 2 (2-Py) S 37

Et Ph 9 SO 2 (2-Py) S 38

SO 2 (2-Py) O O 10 S 39

SO 2 (2-Py) 11 S 40

SO 2 (2-Py) 12 O S 41

SO 2 (2-Py) 13 S 42

Ph Ph Me 14 S 43