Supporting Information

Supporting Information rganocatalytic Enantioselective Formal [4+2] Cycloaddition of Enones with Cyclic N-Sulfonylies and Methylene Chromene for Chiral Spirocyclic Compounds Jie Fei, Qingqing Qian, Xiaohua Sun, Xiaodong Gu, Chuncheng Zou, and Jinxing Ye *, Engineering Research Center of Pharmaceutical Process Chemistry, Ministry of Education, School of Pharmacy, East China University of Science and Technology, 13 Meilong Road, Shanghai 2237, China. A: General Information and Starting Materials... S2 B: Experimental Details... S3 C: Characterization of Products... S5 D: NMR Spectra and HPLC chromatograms of Products... S19 E: Crystallographic Information for Product 3p... S87 F: Crystallographic Information for Product 8d... S1 S1

A: General Information and Starting Materials General Information. Proton nuclear magnetic resonance ( 1 H NMR) spectra and carbon nuclear magnetic resonance ( 13 C NMR) spectra were recorded on a Bruker AV-4 spectrometer (4 MHz and 1 MHz). Chemical shifts for protons are reported in parts per million downfield from tetramethylsilane and are referenced to residual protium in the NMR solvent (CDCl 3 : δ 7.26) Chemical shifts for carbon are reported in parts per million downfield from tetramethylsilane and are referenced to the carbon resonances of the solvent (CDCl 3 : δ 77.16). Data are represented as follows: chemical shift, integration, multiplicity (br = broad, s = singlet, d = doublet, dd = double doublet, t = triplet, q = quartet, m = multiplet), coupling constants in Hertz (Hz). High resolution mass spectrometry (EI) was carried out using a Waters Micromass GCT spectrometer. ptical rotations were measured on an Autopol III automatic polarimeter (Rudolph Research analytical). Enantiomeric excess was detered by chiral HPLC using Agilent 12 Series, Chiralpak IA (.46cm x 25 cm), IC (.46cm x 25 cm), Chiralpak AY (.46cm x 25 cm) and Chiralpak AY (.46cm x 25 cm). Starting Materials. All solvents and inorganic reagents were from commercial sources and used without purification unless otherwise noted. N-Sulfonylies was synthesized following the literature procedure [1]. Substrate enones were synthesized following the literature procedure [2]. 7-hydroxy-2,4-dimethylbenzo[h]chromen-1-ium perchlorate was synthesized following the literature procedure [3]. References [1] a) Q.-R. Zhang, J.-R. Huang, W. Zhang and L. Dong, rg. Lett. 214, 16, 1684-1687; b) Wang, Y. Q.; Yu, C. B.; Wang, D. W.; Wang, X. B.; Zhou, Y.-G. rg. Lett. 28, 1, 271-274. [2] a) K. Zumbansen, A. Döhring, B. List, Adv. Synth. Catal. 21, 352, 1135-1138; b) J. E. Wilson, G. C. Fu, Angew. Chem. Int. Ed. 26, 45, 1426-1429. [3] V. V. Mezheritskii, R. V. Tyurin, L. G. Minyaeva, A. N. Antonov, A. P. Zadorozhnaya, Russ. J. rg. Chem. 26, 42, 1458-1463. S2

B: Experimental Details a) General procedure for formal [4+2] cycloaddition reaction Catalyst (.1 mmol,.5 equiv.) and benzoic acid (.1 mmol,.5equiv.) were added to a solution of 2 (.4 mmol, 2. equiv) in EtAc (.4 ml), 1 (.2 mmol, 1. equiv) was added then. The mixture was stirred at room temperature for indicated time and then the solvent was removed under vacuum. The residue was purified by silica gel chromatography to afford the desired product. The enantiomeric ratio was detered by HPLC analysis on chiral column. b). solvent screening using an ae 4c a. entry solvent conv (%) b ee (%) c 1 DCM 87 97 2 TCM 9 95 3 MeCN 75 94 4 THF full 96 5 Dioxane 6 97 6 EtAc full 97 a reactions were performed with 1a (.1 mmol), 2a (.2 mmol), and cat. (.2 mmol) in solvent (.2 ml). b Detered by GC analysis. c Detered by HPLC analysis on a chiral stationary phase. c). additive screening using an ae 4c in EtAc a S3

entry additive conv (%) b ee (%) c 1 (o-f)c 6 H 4 C 2 H full 96 2 (o-me)c 6 H 4 C 2 H 92 96 3 TsH. H 2 87 95 4 AcH 7 96 5 N-Boc-D-Phg full 97 6 N-Boc-L-Phg full 95 7 Et 3 N trace n.d. a reactions were performed with 1a (.1 mmol), 2a (.2 mmol), and cat. (.2 mmol) in EtAc (.2 ml). b Detered by GC analysis. c Detered by HPLC analysis on a chiral stationary phase. d). catalyst loading screening using an ae 4c/benzoic acid combination in EtAc a entry a x conv (%) b ee (%) c 1 1 full 97 2 5 89 96 3 d 5 74 96 a reactions were performed with 1a (.1 mmol), 2a (.2 mmol), and cat. in EtAc (.2 ml). b Detered by GC analysis. c Detered by HPLC analysis on a chiral stationary phase. d reaction were performed with 1a (.1 mmol), 2a (.15 mmol). S4

C: Characterization of Products S 2 3a, the product was obtained in 9% yield,.62 g, colorless oil. [α] 25 D = 5.5 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7. 7.34-7.26 (m, 4H), 7.25-7.19 (m, 4H), 6.96 (d, J = 8.4 Hz, 1H), 6. (s, 1H), 3.63-3.55 (m, 1H), 3.5 (d, J = 14.4 Hz, 1H), 2.89-2.84 (m, 2H), 2.7 (d, J = 8.8 Hz, 2H), 2.28-2.21 (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 38.22, 43.93, 47.41, 52.29, 65.12, 119.69, 125.6, 125.94, 126.1, 126.76, 127.22, 128.9, 13.19, 142.19, 149.77, 26.77. HRMS(EI) calcd for C 18 H 17 N 4 S [M] + 343.878, found: 343.875; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 9. (major) and 11.8 (or). 3b, the product was obtained in 9% yield,.68 g, white solid. Mp 133-134 C; [α] 25 D = -3.3 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.36-7.24 (m, 6H), 7.2 (d, J = 8.4 Hz, 1H), 7.3 (d, J = 8.4 Hz, 1H), 5.7 (s, 1H), 3.65-3.57 (m, 1H), 3.7 (d, J = 14.8 Hz, 1H), 2.92-2.86 (m, 2H), 2.76-2.62 (m, 2H), 2.19 (dd, J = 14.4, 12.8 Hz, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 37.58, 43.69, 47.24, 52.11, 64.97, 119.68, 124.92, 126.1, 126.6, 128.15, 129., 13.27, 132.9, 14.69, 149.75, 26.77. HRMS(EI) calcd for C 18 H 16 ClN 4 S [M] + 377.489, found: 377.487; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 9.6 (major) and 14.2 (or). S 2 Br 3c, the product was obtained in 85% yield,.71 g, white solid. Mp S5

151-152 C; [α] 25 D = -1.6 (c =.5 in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.42 (s, 1H), 7.4-7.32 (m, 3H), 7.29-7.27 (m, 1H), 7.22-7.2 (m, 1H),7.7 (dd, J = 8., 1.2 Hz, 1H), 5.12 (s, 1H), 3.66-3.58 (m, 1H), 3.1 (d, J = 14.8 Hz, 1H), 2.97-2.92 (m, 1H), 2.84-2.76 (m, 2H), 2.7-2.63 (m, 1H), 2.25-2.18 (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 37.94, 43.48, 47.21, 52.52, 65.1, 119.78, 122.94, 124.77, 125.82, 126.2, 126.6, 129.67, 13.38, 13.4, 13.51, 144.43, 149.74, 25.57. HRMS(EI) calcd for C 18 H 16 BrN 5 S [M] + 42.9983, found: 42.9986; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 7.9 (major) and 21.1 (or). S 2 Br 3d, the product was obtained in 86% yield,.72 g, white solid. Mp 151-152 C; [α] 25 D = -2.8 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.45 (d, J = 8.4 Hz, 2H), 7.38-7.25 (m, 3H), 7.15 (d, J = 8.4 Hz, 2H), 7.6 (d, J = 8.4 Hz, 2H), 5.35 (s, 1H), 3.65-3.57 (m, 1H), 3.9 (d, J = 14.4 Hz, 1H), 2.92 (dd, J = 14., 1.6 Hz, 1H), 2.85-2.81 (m, 1H), 2.78-2.73 (m, 1H), 2.69-2.62 (m, 1H), 2.19 (dd, J = 13.6, 12.8 Hz, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 37.7, 43.61, 47.2, 52.35, 64.98, 119.75, 12.99, 124.85, 125.99, 126.2, 128.5, 13.32, 131.98, 141.16, 149.76, 26.8. HRMS(EI) calcd for C 18 H 16 BrN 4 S [M] + 42.9983, found: 42.9988; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 11. (major) and 15.8 (or). S 2 F 3e, the product was obtained in 85% yield,.61 g, white solid. Mp 13-14 C; [α] 25 D = 1.4 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.37-7.31 (m, 2H), 7.28-7.2 (m, 3H), 7.12-7.8 (m, 1H),7.6-7.2 (m, 2H), 5.67 (s, 1H), 3.85-3.77 (m, 1H), 3.7 (d, J = 14.8 Hz, 1H), 2.95-2.91 (m, 1H), 2.86-2.8 (m, 2H), 2.75-2.71 (m, 1H), 2.5-2.44 (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 33.74, 41.38, 45.98, 52.25, 65.2, 115.96, 116.18, 119.65, 124.6, 124.63, 125.1, 125.97, 126.26, 128.46, 128.62, 128.67, 128.79, 128.85, 128.94, 13.17, 149.75, 159.86, 162.3, 26.62. HRMS(EI) calcd for C 18 H 16 FN 4 S [M] + 361.784, found: 361.782; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow S6

.7 ml/, detection at 21nm) retention time = 9.4 (major) and 18.8 (or). 3f, the product was obtained in 92% yield,.69 g, white solid. Mp 115-116 C; [α] 25 D = 2.4 (c =.5 in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.35-7.31 (m, 2H), 7.26-7.22 (m, 1H), 7.19-7.17 (m, 2H), 7.14 (d, J = 8.4 Hz, 1H), 7.2 (dd, J = 8.4,.8 Hz, 1H), 6.85 (d, J = 8.8 Hz, 2H), 5.61 (s, 1H), 3.77 (s, 3H), 3.6-3.52 (m, 1H), 3.4 (d, J = 14.4 Hz, 1H), 2.88 (dd, J = 14.4, 2. Hz, 3H), 2.76-2.62 (m, 2H), 2.21 (dd, J = 14.4, 12.8 Hz, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 37.48, 44.18, 47.73, 52.25, 55.34, 65.8, 114.24, 119.68, 125.11, 125.93, 126.1, 127.71, 13.16, 134.33, 149.76, 158.64, 26.81. HRMS(EI) calcd for C 19 H 19 N 5 S [M] + 373.984, found: 373.982; HPLC (DAICEL Chiralpak AS, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 19. (or) and 31. (major). S 2 3g, the product was obtained in 89% yield,.66 g, white solid. Mp 162-163 C; [α] 25 D = 29.4 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.35-7.31 (m, 2H), 7.27-7.18 (m, 3H), 7.5-7.2 (m, 1H), 6.96-6.92 (m, 1H), 6.88 (d, J = 8. Hz, 1H), 5.18 (s, 1H), 3.95-3.87 (m, 1H), 3.84 (s, 3H), 3.3-2.95 (m, 2H), 2.83-2.7 (m, 3H), 2.44-2.38 (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 32.86, 41.96, 45.82, 52.29, 55.34, 65.25, 11.81, 119.61, 12.74, 125.23, 125.86, 126.37, 126.81, 128.2, 129.99, 13.7, 149.68, 157.3, 27.28. HRMS(EI) calcd for C 19 H 19 N 5 S [M] + 373.984, found: 373.985; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 9.8 (major) and 13.9 (or). S7

3h, the product was obtained in 94% yield,.67 g, white solid. Mp 132-133 C; [α] 25 D = 1.5 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.35-7.31 (m, 2H), 7.26-7.24 (m, 1H), 7.17-7.12 (m, 4H), 7.3 (dd, J = 8.4,.8 Hz, 1H), 5.56 (s, 1H), 3.62-3.54 (m, 1H), 3.5 (d, J = 14. Hz, 1H), 2.88 (d, J = 14. Hz, 2H), 2.77-2.64 (m, 2H), 2.31 (s, 3H), 2.26-2.19 (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 21.1, 37.83, 44.2, 47.58, 52.24, 65.13, 119.67, 125.12, 125.92, 126.13, 126.61, 129.54, 13.14, 136.84, 139.25, 149.76, 26.98. HRMS(EI) calcd for C 19 H 19 N 4 S [M] + 357.135, found: 357.138; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 1.4 (major) and 2.9 (or). S 2 NC 3i, the product was obtained in 84% yield,.62 g, white solid. Mp 139-14 C; [α] 25 D = -8.4 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.6 (d, J = 8.4 Hz, 2H), 7.4 (d, J = 8.4 Hz, 2H), 7.36-7.33 (m, 2H), 7.28-7.25 (m, 1H),7.4-7.1 (m, 1H), 5.92 (s, 1H), 3.75-3.67 (m, 1H), 3.12 (d, J = 14.8 Hz, 1H), 2.93 (d, J = 14. Hz, 2H), 2.74-2.71 (m, 2H), 2.28-2.21 (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 38.15, 43.22, 46.57, 51.92, 64.87, 11.98, 118.71, 119.65, 124.73, 126.9, 127.76, 129.9, 13.39, 132.74, 147.67, 149.74, 26.36. HRMS(EI) calcd for C 19 H 16 N 2 4 S [M] + 368.831, found: 368.833; HPLC (DAICEL Chiralpak AS, hexane/ EtH = 4/1, flow.7 ml/, detection at 21nm) retention time = 3.8 (major) and 34.7 (or). 3j, the product was obtained in 95% yield,.74 g, yellow solid. Mp 164-165 C; [α] 25 D = -5.1 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.36-7.31 (m, 2H), 7.29-7.27 (m, 1H), 7.25-7.23 (m, 1H),7.6-7.4 (m, 1H), 6.75 (d, J = 8. Hz, 2H), 6.71 (dd, J = 8., 1.6 Hz, 1H), 5.92 (s, 2H), 5.42 (s, 1H), S8

3.58-3.5 (m, 1H), 3.5 (d, J = 14.8 Hz, 1H), 2.9-2.83 (m, 2H), 2.75-2.71 (m, 1H), 2.66-2.59 (m, 1H), 2.19 (dd, J = 14.4, 12.8 Hz, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 37.95, 44.7, 47.34, 52.9, 64.96, 11.8, 17.18, 18.48, 119.62, 119.76, 125.1, 125.92, 126.8, 13.14, 136.17, 146.52, 147.92, 149.71, 26.97. HRMS(EI) calcd for C 19 H 17 N 6 S [M] + 387.777, found: 387.774; HPLC (DAICEL Chiralpak AS, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 23.9 (or) and 34.7 (major). 3k, the product was obtained in 7% yield,.52 g, yellow oil. [α] 25 D = -7.3 (c =.7 in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.34-7.22 (m, 8H), 7.5 (d, J = 8. Hz, 1H), 6.47 (d, J = 15.6 Hz, 1H), 6.14 (dd, J = 16., 6.8 Hz, 1H), 5.48 (s, 1H), 3.23-3.21 (m, 1H), 2.98 (d, J = 14.4 Hz, 1H), 2.84 (d, J = 14.4 Hz, 2H), 2.7 (dd, J = 14.4, 2. Hz, 1H), 2.46-2.4 (m, 1H), 2.9-2.2 (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 36.6, 42.21, 46.47, 52.45, 65.2, 119.72, 124.92, 125.97, 126.13, 126.2, 127.64, 128.61, 127.64, 128.61, 13.19, 13.3, 13.8, 136.61, 149.67, 26.21. HRMS(EI) calcd for C 2 H 19 N 4 S [M] + 369.135, found: 369.136; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 11.3 (major). S 2 3l, the product was obtained in 74% yield,.42 g, white solid. Mp 151-152 C; [α] 25 D = 18.7 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.36-7.32 (m, 1H), 7.3-7.24 (m, 2H), 7.3 (d, J = 8. Hz, 1H), 5.38 (s, 1H), 2.9-2.79 (m, 2H), 2.66 (d, J = 14. Hz, 1H), 2.57-2.52 (m, 1H), 2.48-2.41 (m, 1H), 2.16-2.9 (m, 1H), 1.83 (dd, J = 14., 12. Hz, 1H), 1.11 (d, J = 6.4 Hz, 3H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 21.6, 28.3, 44.44, 48.89, 52.7, 65.28, 119.61, 125.27, 128.89, 126.23, 13.1, 149.69, 27.41. HRMS(EI) calcd for C 13 H 15 N 4 S [M] + 287.722, found: 287.721; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 11.8 (major) and 18.4 (or). S9

S 2 3m, the product was obtained in 64% yield,.36 g, pale yellow oil. [α] 25 D = -27.5 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.82(dd, J = 8., 1.2 Hz, 1H), 7.76-7.72 (m, 1H), 7.44-7.39 (m, 1H), 7.32 (dd, J = 8.4, 1.2 Hz, 1H), 3.2 (d, J = 6.8 Hz, 2H), 2.94-2.77 (m, 1H), 2.63 (dd, J = 18., 7.2 Hz, 1H), 2.42-2.34 (m, 2H),2.29-2.19 (m, 1H), 1.96 (dd, J = 18., 11.2 Hz, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 29.31, 33.55, 38.2, 4.94, 44.6, 116.3, 119.38, 126.1, 127.75, 137.22, 153.54, 178.16, 217.42; HRMS(EI) calcd for C 13 H 13 N 4 S [M] + 279.565, found: 279.654; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 26.3 (mnior) and 29. (major). 3n, the product was obtained in 97% yield,.57 g, colorless solid. Mp 94-95 C; [α] 25 D = -24.3 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.79 (dd, J = 8., 1.6 Hz, 1H), 7.76-7.71 (m, 1H), 7.43-7.39 (m, 1H), 7.32 (dd, J = 8.4,.8 Hz, 1H), 3.9-2.99 (m, 2H), 2.56-2.51 (m, 2H), 2.44-2.39 (m, 1H),2.34-2.17 (m, 2H), 2.11-2.6 (m, 2H), 1.78-1.67 (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 24.67, 3.87, 36.12, 41.11, 41.84, 47.44, 116.4, 119.33, 126.9, 128.4, 137.32, 153.54, 178.17, 29.87. HRMS(EI) calcd for C 14 H 15 N 4 S [M] + 293.722, found: 293.721; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 28.4 (or) and 33.1 (major). 3o, the product was obtained in 7% yield,.43 g, colorless oil. [α] 25 D = -3.3 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.81 (dd, J = 8., 1.6 Hz, 1H), 7.75-7.71 (m, 1H), 7.42-7.38 (m, 1H), 7.31 (dd, J = 8.,.8 Hz, 1H), 3.5 (dd, J = 16., 5.6 Hz, 1H), 2.96 (dd, J = 16.4, 7.2 Hz, 1H), 2.69-2.65 (m, 1H), 2.61-2.47 (m, 4H), 1.98-1.86 (m, 3H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 24.25, 27.97, 32.99, 36.15, 42.8, 43.82, 49.33, 116.25, 119.39, 126.1, 127.94, 137.17, 153.65, 178.31, 212.78. HRMS(EI) calcd for C 15 H 17 N 4 S [M] + 37.878, found: S1

37.877; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 26.1 (or) and 36. (major). S 2 S 3p, the product was obtained in 75% yield,.52 g, white solid. Mp 138-139 C; [α] 25 D = 6.2 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.37-7.33 (m, 1H), 7.33-7.29 (m, 2H), 7.28-7.26 (m, 1H), 7.7-7.1 (m, 3H), 5.33 (s, 1H), 3.76-3.68 (m, 1H), 3.7-2.99 (m, 2H), 2.89-2.83 (m, 2H), 2.68-2.61 (m, 1H), 2.2 (dd, J = 14.4, 12.4 Hz, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 33.8, 43.39, 47.35, 52.34, 64.9, 119.85, 124.88, 125.95, 126.1, 126.33, 126.4, 13.21, 143.38, 149.71, 26.41. HRMS(EI) calcd for C 16 H 15 N 4 S 2 [M] + 349.442, found: 349.445; HPLC (DAICEL Chiralpak AS, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 39.7 (major). S 2 3q, the product was obtained in 75% yield,.5 g, orange oil. [α] 25 D = 4.5 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.38-7.28 (m, 4H), 7.6 (d, J = 8.4 Hz, 1H), 6.3-6.29 (m, 1H), 6.9 (d, J = 3.2 Hz, 1H), 5.45 (s, 1H), 3.74-3.66 (m, 1H), 3.5-2.97 (m, 2H), 2.88-2.8 (m, 2H), 2.72-2.66 (m, 1H), 2.35-2.28 (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 32.25, 4.79, 45.14, 52.37, 64.7, 14.99, 11.23, 119.67, 124.74, 125.98, 126.2, 13.22, 141.74, 149.67, 155.28, 26.14. HRMS(EI) calcd for C 16 H 15 N 5 S [M] + 333.671, found: 333.674; HPLC (DAICEL Chiralpak AS, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 22.9 (or) and 28.1 (major). 3r, the product was obtained in 93% yield,.73 g, white solid. Mp 124-125 C; [α] 25 D = -2.4 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.8-7.77 (m, 3H), 7.67 (s, 1H), 7.48-7.42 (m, 2H), 7.39 (dd, J = 8.4, 1.6 Hz, 1H), 7.35-7.3 (m, 2H), 7.26-7.22 (m, 2H), 7.3 (dd, J = 8., 1.2 Hz, 1H), 5.66 (s, S11

1H), 3.83-3.74 (m, 1H), 3.9 (d, J = 14.4 Hz, 1H), 3. (d, J = 14.4 Hz, 1H), 2.91 (d, J = 14.4 Hz, 1H), 2.86-2.77 (m, 2H), 2.32 (dd, J = 14., 12.4 Hz, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 38.28, 43.78, 47.38, 52.3, 55.15, 119.69, 124.97, 125.7, 125.34, 125.91, 125.98, 126.14, 126.37, 127.67, 127.72, 128.64, 13.21, 132.57, 133.51, 139.64, 149.79, 26.95. HRMS(EI) calcd for C 22 H 19 N 4 S [M] + 393.135, found: 393.136; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 1.7 (major) and 21. (or). F S 2 3s, the product was obtained in 83% yield,.6 g, white solid. Mp 126-127 C; [α] 25 D = 7.7 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7. 7.35-7.31 (m, 2H), 7.27-7.23 (m, 3H), 7.7-7. (m, 3H), 3.65-3.57 (m, 1H), 3. (d, J = 14.4 Hz, 1H), 2.91 (d, J = 14.4 Hz, 2H), 2.75-2.71 (m, 2H), 2.24-2.18 (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 38.17, 43.7, 47.35, 51.93, 64.99, 112.81, 113.6, 117.14, 117.37, 121.24, 121.32, 126.63, 126.69, 126.76, 126.86, 127.3, 128.94, 141.97, 145.59, 158.36, 16.81, 26.81. HRMS(EI) calcd for C 18 H 16 FN 4 S [M] + 361.784, found: 361.785; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 7.2 (major) and 23.9 (or). Br S 2 3t, the product was obtained in 87% yield,.73 g, white solid. Mp 143-144 C; [α] 25 D = 53.3 (c =.4 in CH 2 Cl 2 ); 1 H-NMR (4 MHz, d 6 -DMS): δ (ppm) 8.86 (s, 1H), 8.1 (d, J = 2. Hz, 1H), 7.58 (dd, J = 8.8, 6.4 Hz, 1H), 7.42 (d, J = 7.2 Hz, 2H), 7.35 (t, J = 7.6 Hz, 2H), 7.24 (t, J = 7.2 Hz, 1H), 7.12 (d, J = 8.8 Hz, 1H), 3.41-3.35 (m, 1H), 3.24 (d, J = 14. Hz, 1H), 2.99 (d, J = 14. Hz, 1H), 2.94-2.87 (m, 1H), 2.74 (t, J = 13.2 Hz, 1H) 2.46-2.43 (m, 1H), 2.37 (d, J = 13.6 Hz, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 38.21, 43.79, 47.37, 52.15, 64.94, 118.6, 121.45, 126.75, 126.91, 127.34, 128.96, 129.14, 133.24, 141.88, 148.82, 26.31. HRMS(EI) calcd for C 18 H 16 BrN 4 S [M] + 42.9983, found: 42.9981; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 4/1, flow.7 ml/, detection at 21nm) retention time = 8.4 (major) and 1.6 (or). S12

S 2 3u, the product was obtained in 81% yield,.6 g, white solid. Mp 1-11 C; [α] 25 D = 1.4 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7. 7.34-7.31 (m, 2H), 7.27-7.19 (m, 4H), 6.79 (dd, J = 8.8, 6. Hz, 1H), 6.52 (d, J = 2.4 Hz, 1H), 5.59 (s, 1H), 3.78 (s, 3H), 3.63-3.55 (m, 1H), 3.1 (d, J = 14.4 Hz, 1H), 2.86 (d, J = 13.6 Hz, 2H), 2.77-2.65 (m, 2H), 2.24-2.17 (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 38.13, 44.9, 47.39, 52.44, 55.72, 64.83, 13.99, 112.93, 116.91, 126.77, 126.81, 127.16, 128.88, 142.32, 15.48, 16.52, 27.25. HRMS(EI) calcd for C 19 H 19 N 5 S [M] + 373.984, found: 373.987; HPLC (DAICEL Chiralpak AY hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 12.3 (major) and 23.3 (or). S 2 3v, the product was obtained in 8% yield,.57 g, white solid. Mp 176-177 C; [α] 25 D = 24.3 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.35-7.32 (m, 2H), 7.29-7.23 (m, 3H), 7.14-7.1 (m, 2H), 6.93 (d, J = 8.4 Hz, 1H), 5.22 (s, 1H), 3.66-3.58 (m, 1H), 3.7 (d, J = 14.4 Hz, 1H), 2.92-2.88 (m, 1H), 2.87-2.82 (m, 1H), 2.81-2.67 (m, 1H), 2.36 (s, 3H), 2.24 (dd, J = 14., 12.4 Hz, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 2.96, 38.22, 43.87, 47.41, 52.44, 65.11, 119.38, 124.48, 126.3, 126.73, 127.17, 128.86, 13.79, 135.73, 142.2, 147.58, 26.58. HRMS(EI) calcd for C 19 H 19 N 4 S [M] + 357.135, found: 357.14; HPLC (DAICEL Chiralpak AS, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 13.3 (or) and 18.6 (major). Cl S 2 3w, the product was obtained in 87% yield,.66 g, white solid. Mp 139-14 C; [α] 25 D = 33.1 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.35-7.23 (m, 7H), 6.99 (d, J = 8.4 Hz, 1H), 5.78 (s, 1H), 3.64-3.56 (m, 1H), 3.2 (d, J = 14. Hz, 1H), 2.91 (d, J = 14. Hz, 2H), 2.79-2.68 (m, 2H), 2.25-2.19 (m, S13

1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 38.16, 43.74, 47.35, 51.96, 64.98, 121.1, 126.25, 126.59, 126.76, 127.31, 128.94, 13.26, 131.14, 141.94, 148.26, 26.8. HRMS(EI) calcd for C 18 H 16 ClN 4 S [M] + 377.489, found: 377.487; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 7.1 (major) and 1.7 (or). 3x, the product was obtained in 9% yield,.62 g, yellow solid. Mp 132-133 C; [α] 25 D = -1.2 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 8.18-8.13 (m, 2H), 7.97 (d, J = 8. Hz, 1H), 7.77-7.73 (m, 1H), 7.66-7.62 (m, 1H), 7.37(d, J = 9.2 Hz, 1H), 3.39-3.28 (m, 2H), 2.65-2.61 (m, 1H), 2.47 (d, J = 14. Hz, 1H), 2.36 (d, J = 14.4 Hz, 1H ), 2.24-2.16 (m, 1H), 2.1-2.3 (m, 1H), 1.97-1.95 (m, 2H), 1.71-1.61 (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 24.54, 3.64, 36.96, 41.5, 46.65, 47.26, 114.9, 117.43, 125.34, 126.95, 129., 129.67, 13.7, 131.61, 138.99, 154.54, 181.26, 29.91. HRMS(EI) calcd for C 18 H 17 N 4 S [M] + 343.878, found: 343.875; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 3.3 (or) and 56.8 (major). 3y, the product was obtained in 8% yield,.58 g, white solid. Mp 13-131 C; [α] 25 D = 3.3 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.35-7.23 (m, 6H), 7.1-6.96 (m, 1H), 6.78 (dd, J = 8.4, 2.4 Hz, 1H), 5.66, (s, 1H), 3.65-3.57 (m, 1H), 3.3 (d, J = 14.4 Hz, 1H), 2.92-2.87 (m, 2H), 2.8-2.67 (m, 2H), 2.25-2.18 (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 38.14, 44.6, 47.35, 52.36, 64.88, 17.13, 17.38, 113.28, 113.5, 121.7, 121.1, 126.72, 127.29, 127.45, 127.55, 128.94, 142., 15.41, 15.53, 161.18, 163.68, 26.76. HRMS(EI) calcd for C 18 H 16 FN 4 S [M] + 361.784, found: 361.783; HPLC (DAICEL Chiralpak IA, hexane/ dichloromethane = 7/3, flow 1. ml/, detection at 24nm) retention time = 12. (or) and 14.3 (major). S14

2 S 5a, the product was obtained in 83% yield,.54 g, white solid. Mp 196-197 C; [α] 25 D = 1.6 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, d 6 -DMS): δ (ppm) 8.29 (s, 1H), 7.89 (d, J = 8. Hz, 1H), 7.83 (d, J = 7.6 Hz, 1H), 7.79-7.75(m, 1H), 7.61 (t, J = 7.6 Hz, 1H), 7.4 (d, J = 7.6 Hz, 2H), 7.35 (t, J = 7.6 Hz, 2H), 7.23 (t, J = 7.2 Hz, 2H), 3.5-3.46 (m, 1H), 3.2 (d, J = 14.4 Hz, 1H), 2.9 (t, J = 13.6 Hz, 1H), 2.81 (t, J = 13.2 Hz, 1H), 2.51-2.47 (m, 2H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 4.34, 44.39, 47.71, 51.29, 65.65, 121.68, 122.85, 126.68, 127.29, 128.92, 129.98, 133.65, 135.87, 142.15, 143.35, 26.28. HRMS(EI) calcd for C 18 H 17 N 3 S [M] + 327.929, found: 327.928; HPLC (DAICEL Chiralpak AS, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 17.7 (or) and 3.1 (major). 5b, the product was obtained in 74% yield,.39 g, white solid. Mp 195-196 C; [α] 25 D = 11.5 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.76 (d, J = 7.6 Hz, 1H), 7.68 (t, J = 7.2 Hz, 1H), 7.56 (t, J = 7.6 Hz, 1H), 7.46 (d, J = 8. Hz, 1H), 5.21 (s, 1H), 2.9 (d, J = 14.4 Hz, 1H), 2.61-2.54 (m, 2H), 2.44-2.32 (m, 1H), 2.22-2.11 (m, 2H), 1.91-1.84 (m, 1H), 1.12 (d, J = 6.4 Hz, 3H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 21.8, 3.6, 44.98, 48.85, 51.23, 65.81, 121.55, 122.88, 129.83, 133.6, 135.65, 143.44, 27.4. HRMS(EI) calcd for C 13 H 15 N 3 S [M] + 265.773, found: 265.778; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 19.1 (major) and 34.2 (or). 5c, The product was obtained in 6% yield,.33 g, white solid. Mp 141-142 C; [α] 25 D = -9.5 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.94-7.92 (m, 1H), 7.79-7.73 (m, 2H), 7.69-7.67 (m, 1H), 3.-2.98 (m, 2H), S15

2.64-2.59 (m, 2H), 2.46-2.41 (m, 1H), 2.35-2.22 (m, 2H), 2.14-2.5 (m, 2H), 1.81-1.69 (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 24.66, 3.86, 35.79, 37.7, 41.15, 47.64, 122.66, 123.86, 131.14, 133.8, 134.2, 139.7, 173.96, 29.78. HRMS(EI) calcd for C 14 H 15 N 3 S [M] + 277.773, found: 277.779; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 49.9 (or) and 58.2 (major). 2 S F 5d, the product was obtained in 77% yield,.53 g, white solid. Mp 161-162 C; [α] 25 D = -.5 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.76 (d, J = 7.6 Hz, 1H), 7.69-7.66 (m, 1H), 7.54 (dd, J = 14., 7.6 Hz, 1H), 7.31-7.25 (m, 1H), 7.5 (d, J = 7.6 Hz, 1H), 5.62 (s, 1H), 3.61-3.53 (m, 1H), 3.8 (d, J = 14.8 Hz, 1H), 2.78-2.65 (m, 3H), 2.34-2.31 (m, 2H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 39.87, 44.1, 47.41, 51.1, 65.5, 113.52, 113.74, 114.4, 114.24, 121.61, 122.58, 122.6, 122.95, 13.1, 13.4, 13.49, 133.72, 135.8, 143.29, 144.81, 144.88, 161.82, 164.27, 26.32. HRMS(EI) calcd for C 18 H 16 FN 3 S [M] + 345.835, found: 345.837; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 14.3 (major) and 23.6 (or). 5e, the product was obtained in 68% yield,.4 g, colorless oil. [α] 25 D = 18.6 (c =.8 in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) 7.94-7.92 (m, 1H), 7.79-7.72 (m, 2H), 7.69-7.67 (m, 1H), 3.1-2.89 (m, 2H), 2.74-2.71 (m, 1H), 2.68-2.48 (m, 4H), 2.5-1.87 (m, 3H), 1.7-1.6 (m, 2H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 24.3, 28.3, 32.8, 36.23, 37.65, 43.85, 49.5, 122.62, 123.87, 131.25, 133.75, 133.99, 139.71, 174.38, 212.69. HRMS(EI) calcd for C 15 H 17 N 3 S [M] + 291.929, found: 291.93; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 45.8 (or) and 66.5 (major). S16

8a, the product was obtained in 52% yield,.19 g, colorless oil. [α] 25 D = -47.8 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, d 6 -DMS): δ (ppm) 1.17 (s, 1H), 7.84 (d, J = 9.2 Hz, 1H), 7.71 (d, J = 8.8 Hz, 1H), 7.53 (d, J = 8.4 Hz, 1H), 7.38-7.36 (m, 2H), 7.33-7.28 (m, 3H), 7.22-7.17 (m, 1H), 6.89-6.87 (m, 1H), 4.99 (s, 1H), 3.42-3.38 (m, 1H), 3.3 (d, J = 13.2 Hz, 1H), 2.9 (t, J = 13.2 Hz, 1H), 2.6 (t, J = 13.2 Hz, 1H), 2.4-2.37 (m, 1H), 2.29 (d, J = 12.8 Hz, 1H), 2.1 (s, 3H), 1.85 (d, J = 12.8 Hz, 1H). 13 C-NMR (1 MHz, d 6 -DMS): δ (ppm) 19.48, 38.13, 39.28, 47.67, 48.13, 55.39, 11.51, 19.27, 112.18, 117.56, 12.92, 122.92, 124.48, 124.97, 126.98, 127.13, 127.34, 127.44, 128.97, 144.75, 144.81, 146.13, 146.98, 153.5, 28.81. HRMS(EI) calcd for C 25 H 22 3 [M] + 37.1569, found: 37.1568; HPLC (DAICEL Chiralpak AS, hexane/ EtH = 9/1, flow 1. ml/, detection at 254nm) retention time = 14.1 (or) and 17.2 (major). 8b, the product was obtained in 53% yield,.2 g, colorless oil. [α] 25 D = -65.3 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, d 6 -DMS): δ (ppm) 1.18 (s, 1H), 7.86 (d, J = 8.8 Hz, 1H), 7.71 (d, J = 9.2 Hz, 1H), 7.54 (d, J = 8.8 Hz, 1H), 7.33-7.29 (m, 1H), 7.19-7.15 (m, 3H), 6.99 (d, J = 6.8 Hz, 1H), 6.88 (d, J = 7.2 Hz, 1H), 4.99 (s, 1H), 3.35-3.33 (m, 1H), 3.29 (d, J = 12.8 Hz, 1H), 2.89 (t, J = 13.2 Hz, 1H), 2.58 (t, J = 12.8 Hz, 1H), 2.38-2.35 (m, 1H), 2.26(s, 3H), 2.1 (s, 3H), 1.84 (d, J = 12. Hz, 1H). 13 C-NMR (1 MHz, d 6 -DMS): δ (ppm) 19.48, 21.5, 38.11, 39.28, 47.81, 48.14, 55.36, 11.52, 19.26, 112.19, 117.57, 12.93, 122.92, 124.37, 124.5, 124.99, 127.1, 127.6, 127.97, 128.83, 138.1, 144.67, 144.82, 146.12, 153.52, 28.8. HRMS(EI) calcd for C 26 H 24 3 [M] + 384.1725, found: 384.1726; HPLC (DAICEL Chiralpak IC, hexane/dcm = 1/1, flow 1. ml/, detection at 254nm) retention time = 25.1 (major) and 33.1 (or). S17

8c, the product was obtained in 6% yield,.25 g, colorless oil. [α] 25 D = -113.6 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, d 6 -DMS): δ (ppm) 1.2 (s, 1H), 7.89 (d, J = 8.8 Hz, 1H), 7.85-7.81 (m, 4H), 7.74 (d, J = 9.2 Hz, 1H), 7.56 (d, J = 8.4 Hz, 2H), 7.47-7.4 (m, 2H), 7.34-7.3 (m, 1H), 6.9 (dd, J = 7.6, 6.8 Hz, 1H), 5.6 (s, 1H), 3.61-3.53 (m, 1H), 3.34 (d, J = 12.8 Hz, 1H), 3.1 (t, J = 13.2 Hz, 1H), 2.7 (t, J = 13.2 Hz, 1H), 2.49-2.47 (m, 1H), 2.34 (d, J = 13.2 Hz, 1H), 2.4(s, 3H), 1.98-1.94 (m, 1H). 13 C-NMR (1 MHz, d 6 -DMS): δ (ppm) 19.51, 38.23, 39.3, 47.6, 48.1, 55.39, 11.57, 19.32, 112.22, 117.64, 12.96, 122.98, 124.53, 125.2, 125.37, 125.96, 126.12, 126.52, 127.18, 127.87, 127.97, 128.48, 132.4, 133.59, 142.27, 144.86, 146.21, 153.55, 28.73. HRMS(EI) calcd for C 29 H 24 3 [M] + 42.1725, found: 42.1723; HPLC (DAICEL Chiralpak IA, hexane/ DCM = 1/1, flow 1. ml/, detection at 254nm) retention time = 29.1 (or) and 45.5 (major). 8d, the product was obtained in 46% yield,.17 g, white solid. Mp 181-182 C; [α] 25 D = -88.5 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, d 6 -DMS): δ (ppm) 1.21 (s, 1H), 7.87 (d, J = 8.8 Hz, 1H), 7.69 (d, J = 8.8 Hz, 1H), 7.57 (d, J = 8.4 Hz, 1H), 7.5-7.48 (m, 1H), 7.36-7.32 (m, 2H), 7.18 (d, J = 5.2 Hz, 1H), 6.91 (d, J = 7.2 Hz, 1H), 4.97 (s, 1H), 3.54-3.48 (m, 1H), 3.29 (d, J = 12.8 Hz, 1H), 2.84 (t, J = 13.2 Hz, 1H), 2.53-2.5 (m, 2H), 2.31 (d, J = 12.8 Hz, 1H), 2.3(s, 3H), 2.1 (s, 3H), 2. (d, J = 4. Hz, 1H). 13 C-NMR (1 MHz, d 6 -DMS): δ (ppm) 19.51, 33.56, 39.8, 47.26, 47.89, 55.41, 11.48, 19.3, 112.2, 117.62, 12.44, 12.91, 122.97, 124.51, 125.1, 126.7, 127.2, 127.36, 144.85, 145.89, 146.17, 153.56, 28.63. HRMS(EI) calcd for C 23 H 2 3 S [M] + 376.1133, found: 376.1132; HPLC (DAICEL Chiralpak IA, hexane/ DCM = 1/2, flow.8 ml/, detection at 254nm) retention time = 13.1 (or) and 24.5 (major). S18

D: NMR Spectra and HPLC chromatograms of Products S19

mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14927\FJ54RA-AY.D) 175 15 125 8. 9 1 2 1 75 5 1 6. 5 7 2 25 2.5 5 7.5 1 12.5 15 17.5 2 1 8.912 33661.5 1257.5.3997.418 49.486 2 16.572 34361.3 46 1.2449.488 5.514 mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\1417\FJ553D9.D) 175 15 125 8. 9 6 1 1 75 5 25 2.5 5 7.5 1 12.5 15 17.5 2 1 7. 7 6 8 1 8.961 34151 1295.6.3934.417 98.114 2 17.768 656.5 6.2 1.7685.713 1.886 S2

mau 12 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14116\GTT178F.D) S 2 1 9. 6 8 5 8 6 Cl rac - 3b 1 4. 7 1 4 2 2 4 6 8 1 12 14 16 18 1 9.685 4217.2 919.7.6426.399 49.156 2 14.71 41598.7 454.2 1.5265.654 5.844 mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14116\FJ-565A.D) 2 9. 5 5 8 15 1 5 2 4 6 8 1 12 14 1 4. 2 3 2 1 9.558 8532.7 1772.6.7242.343 97.52 2 14.232 2178.8 21.2 1.7113.856 2.498 S22

mau 16 14 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14119\FJ573RA59.D) S 2 7. 9 1 2 12 1 8 6 Br rac - 3c 4 2 2 2. 7 9 5 1 15 2 25 mau 16 14 1 7.912 2156.8 1353.2.2456.634 49.627 2 22.79 21884.9 12.3 3.5658.554 5.373 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14119\FJ573A6.D) S 2 7. 8 6 1 12 1 8 6 4 Br 3c 2 5 1 15 2 25 2 1. 1 2 3 1 7.861 23991.3 1486.5.248.628 99.777 2 21.123 53.6 1.8.3878 1.48.223 S24

mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14116\FJ565RB.D) 8 S 2 6 4 Br rac - 3d 1 1. 1 3 1 5. 7 7 3 2 2 4 6 8 1 12 14 16 18 mau 8 1 11.13 28659.3 511.5.8182.397 49.52 2 15.773 29767.5 342.8 1.4471.855 5.948 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14116\FJ565B-2.D) S 2 6 1. 9 8 1 4 Br 3d 2 1 5. 7 8 6 2 4 6 8 1 12 14 16 18 1 1.981 3129.2 544.6.8129.41 99.46 2 15.786 29.1 3.6.9637.596.954 S26

mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14116\FJ565RC.D) 12 1 8 S 2 9. 4 5 8 6 4 2 F rac - 3e 1 8. 5 3 2.5 5 7.5 1 12.5 15 17.5 2 mau 12 1 9.458 2446.4 146.4.3453.521 49.74 2 18.53 24297.6 287.5 1.2814.649 5.26 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14116\FJ565C.D) S 2 9. 4 4 2 1 8 6 F 3e 4 2 2.5 5 7.5 1 12.5 15 17.5 2 1 8. 7 5 8 1 9.442 25937.7 1148.5.3421.51 98.32 2 18.758 443.3 5.2 1.8.851 1.68 S28

mau 4 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14118\FJ569RB-AS5.D) S 2 3 2 rac - 3f 1 8. 5 3 6 1 3 1. 2 2 1 5 1 15 2 25 3 35 mau 4 1 18.536 1175.5 171.6 1.393.536 5.63 2 31.221 11721 85.7 1.9652.74 49.937 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14118\FJ569B-AS51.D) S 2 3 2 3f 3 1. 1 3 1 1 8. 9 6 4 5 1 15 2 25 3 35 1 18.964 388.9 5.9352.641 1.717 2 31.13 22262.7 156.5 2.931.582 98.283 S3

mau 8 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14119\FJ573RC62.D) S 2 6 9. 9 5 2 4 2 Me rac - 3g 1 3. 9 1 2 4 6 8 1 12 14 16 1 9.952 14414.3 558.436.586 5.118 2 13.91 14346.5 223.8.9648.79 49.882 mau 2 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14119\FJ573C63.D) S 2 9. 8 9 15 1 Me 3g 5 2 4 6 8 1 12 14 16 1 3. 9 5 1 1 9.89 59173.6 1867.7.4948.438 97.922 2 13.951 1255.5 19.9.9597.698 2.78 S32

mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14118\FJ569RD46.D) 4 3 S 2 1. 4 8 2 2 1 rac - 3h 2. 3 1 3 5 1 15 2 25 mau 7 6 5 1 1.482 166 33.7.7662.387 49.13 2 2.313 1659.6 112.2 2.168.65 5.897 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14118\FJ569D47.D) S 2 1. 4 4 3 3h 2 1 5 1 15 2 25 2. 9 4 1 1.4 26475.4 512.4.7455.359 98.894 2 2.94 296.1 2.4 1.4721 1.18 1.16 S34

mau 25 2 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ576RC-2112.D) S 2 3.8 5 8 15 1 NC rac - 3i 3 3.7 9 5 5 5 1 15 2 25 3 35 4 1 3.858 1789.4 199.6 1.2855.669 49.255 2 33.795 1766.2 94.3 2.5418.434 5.745 mau 4 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ576C113.D) S 2 3.8 7 3 NC 3i 2 1 5 1 15 2 25 3 35 3 4.6 7 9 1 3.87 36964.2 399.7 1.394.569 99.729 2 34.679 1.4 3.4134.861.271 S36

mau 35 3 25 2 15 1 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14128\FJ573RB132.D) rac - 3j S 2 2 2. 2 8 2 3 3. 2 7 8 5 5 1 15 2 25 3 35 4 1 22.282 1856.6 123.4 1.323.496 49.299 2 33.278 11165.1 97.1 1.7315.734 5.71 mau 8 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14119\FJ573B-AS65.D) S 2 6 4 3j 3 4. 6 9 7 2 5 1 15 2 25 3 35 4 2 3. 9 1 1 1 23.911 1168.3 11.1 1.2966.553 1.536 2 34.697 7497.6 496.1 2.5163.494 98.464 S38

mau 12 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ576RB-217.D) S 2 1 8 1 1.3 6 8 rac - 3k 6 4 2 4.2 9 5 5 1 15 2 25 3 35 4 45 mau 8 1 11.368 4232.4 752.4.889.349 49.371 2 4.295 4338.1 136.9 5.2824.683 5.629 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ576B18.D) 1 1.3 7 S 2 6 4 3k 2 5 1 15 2 25 3 35 4 45 1 11.37 3964 734.7.7774.358 1. S4

mau 12 1 8 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\1413\59RA-AS.D) rac - 3l S 2 1 1. 8 8 6 4 1 7. 2 7 1 2 mau 12 2.5 5 7.5 1 12.5 15 17.5 2 22.5 1 11.88 26745.1 925.7.444.481 49.632 2 17.271 27141.7 333.9 1.1856.331 5.368 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\1413\59A-AS.D) S 2 1 8 3l 1 1. 8 1 6 4 2 5 1 15 2 1 8. 3 5 9 1 11.81 25562.2 896.8.4374.485 98.285 2 18.359 446.1 6.8.7879.641 1.715 S42

mau 12 1 8 6 4 2 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14121\FJ574RB8.D) S 2 rac - 3m 2 6. 2 2 6 2 9. 7 3 5 1 15 2 25 3 mau 8 1 26.226 26619.4 758.8.5432.75 5.116 2 29.73 26496.4 659.3.6145.65 49.884 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14121\FJ574B81.D) S 2 6 3m 2 9. 1 4 2 5 1 15 2 25 3 2 6. 3 2 1 26.32 627.9 18.9.521.94 2.657 2 29.1 232.4 574.9.6168.659 97.343 S44

mau 4 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14121\FJ574RA78.D) S 2 3 rac - 3n 2 8. 7 3 7 3 4. 2 1 2 1 5 1 15 2 25 3 35 1 28.737 156.5 259.5.67.767 5.143 2 34.21 9999.3 218.5.728.72 49.857 mau 12 1 8 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14121\FJ574A79.D) 3n S 2 3 3. 1 4 7 6 4 2 5 1 15 2 25 3 35 2 8. 3 7 9 1 28.379 955 25.6.5786.912 1.852 2 33.147 5612.3 15.8.7381.564 98.148 S46

mau 12 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14121\FJ574RC82.D) S 2 1 8 6 rac - 3o 2 5. 8 5 9 3 6. 2 6 3 4 2 5 1 15 2 25 3 35 1 25.859 28663.1 784.4.5632.628 49.984 2 36.263 2868.9 577.4.7659.711 5.16 mau 175 15 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14121\FJ574C83.D) S 2 3 6. 4 2 125 1 rac - 3o 75 5 25 5 1 15 2 25 3 35 2 6. 1 4 2 1 26.142 131 37.2.5452.829 1.699 2 36.42 7583.2 1414.7.822.555 98.31 S48

mau 4 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14127\FJ581RA-AS.D) S 2 3 2 S rac - 3p 2. 2 7 2 3 9. 1 9 4 1 mau 4 5 1 15 2 25 3 35 4 45 1 2.272 31896.5 222 1.9483.263 49.839 2 39.194 3212.8 25.8 2.2847.521 5.161 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14127\FJ581A.D) S 2 3 2 S 3p 3 9. 7 1 6 1 5 1 15 2 25 3 35 4 45 1 39.716 35746.4 216.7 2.3844.539 1. S5

mau 8 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ576RA-AS19.D) S 2 6 4 rac - 3q 2 1. 6 8 4 2 7. 9 6 8 2 5 1 15 2 25 3 mau 7 6 1 21.684 41388.1 268.3 2.1116.22 5.481 2 27.968 4598.9 428.3 1.413.483 49.519 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ576A11.D) S 2 5 4 3 3q 2 8. 1 2 2 1 5 1 15 2 25 3 2 2. 9 6 9 1 22.969 458.7 6.2.8949.768 1.351 2 28.12 33487.3 361 1.3937.511 98.649 S52

mau 12 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14118\FJ569RC44.D) S 2 1 8 6 rac -3r 1. 7 1 2 4 2 2 1. 3 1 5 1 15 2 25 mau 175 15 1 1.712 25511.5 86.4741.543 5.74 2 21.31 25436.5 146.7 2.892.678 49.926 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14118\FJ569C45.D) S 2 1. 6 8 8 125 1 75 3r 5 25 5 1 15 2 25 2. 9 9 9 1 1.688 47816 1459.1.4944.57 99.55 2 2.999 455.9 3.2 1.6699.446.945 S54

mau 175 15 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ579RA114.D) 7.2 9 F S 2 125 1 rac - 3s 75 5 25 2 3.1 7 7 5 1 15 2 25 3 mau 175 15 1 7.29 38731.9 1658.1.3511.47 49.334 2 23.177 39776.8 191.6 2.8194.548 5.666 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ579A115.D) 7.1 5 9 F S 2 125 1 3s 75 5 25 5 1 15 2 25 3 2 3.8 9 1 1 7.159 6888.4 1919.2.5595.289 98.516 2 23.891 136.2 9.6 1.2865 3.14 1.484 S56

mau 7 6 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ579RB-2121.D) Br S 2 5 8. 5 9 4 3 rac - 3t 1.6 1 7 2 1 2 4 6 8 1 12 14 16 1 8.59 15711.4 442.7.5218.454 47.639 2 1.617 17268.8 255.1.9951.531 52.361 mau 2 15 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ579B-2123.D) Br S 2 8. 4 4 6 1 3t 5 2 4 6 8 1 12 1. 5 7 7 1 8.446 58474.3 1575.3.6187 96.944 2 1.577 1843.3 31.9.9635.127 3.56 S58

mau 175 15 125 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ579RC117.D) Me S 2 1 2. 3 7 3 1 75 5 rac - 3u 2 2. 9 3 25 5 1 15 2 25 mau 2 1 12.373 7167 131.6.7971.424 49.187 2 22.93 73416.3 614.8 1.991.822 5.813 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ579C118.D) Me S 2 1 2. 2 5 7 15 1 3u 5 5 1 15 2 25 1 12.257 19785.8 1821.3.922.376 98.53 2 23.284 218.1 17.6 1.4655.93 1.947 2 3. 2 8 4 S6

mau 4 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14127\FJ581RB-AS.D) S 2 3 1 2. 4 2 9 1 8. 7 5 9 2 rac - 3v 1 5 1 15 2 25 1 12.429 2351.7 252 1.1694.361 51.81 2 18.759 1949.4 241.3 1.236.75 48.919 mau 8 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14127\FJ581B.D) S 2 1 8. 5 5 7 6 4 3v 2 2.5 5 7.5 1 12.5 15 17.5 2 22.5 1 13.298 493 6.1.9621.64.835 2 18.557 58531.3 72.3 1.2737.647 99.165 1 3. 2 9 8 S62

mau 7 6 5 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14113\FJ596RB.D) Cl S 2 7. 2 6 4 3 rac - 3w 2 1 1. 8 3 2 2 4 6 8 1 12 14 16 1 7.26 13843.8 521.9.3837.47 5.833 2 1.832 13389.8 121.2 1.5946.538 49.167 mau 175 15 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14113\FJ596B.D) Cl S 2 7. 9 8 125 1 75 3w 5 25 2 4 6 8 1 12 1. 7 3 1 7.98 46245.6 1653.2.4181.47 97.374 2 1.73 1247.2 11.4 1.838 1.156 2.626 S64

mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14128\FJ583RC13.D) 12 1 S 2 2 9. 6 2 6 8 rac - 3x 6 4 5 7. 6 3 2 1 2 3 4 5 6 mau 8 1 29.626 54969.9 19.888.64 49.891 2 57.63 5529.2 424.1 2.1695.39 5.19 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14128\FJ583C131.D) S 2 6 3x 5 6. 8 2 4 2 3. 2 8 1 1 2 3 4 5 6 1 3.281 197 2.9.797.823 1.433 2 56.82 7546.9 538.3 2.3362.386 98.567 S66

mau 175 15 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14114\FJ511RA17.D) F S 2 125 1 75 rac - 3y 1 1. 5 2 1 4. 4 3 8 5 25 2.5 5 7.5 1 12.5 15 17.5 2 22.5 1 11.52 5535.8 195.2.7552.419 48.994 2 14.438 57296.8 93.7.9498.643 51.6 mau 175 15 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14114\FJ511A.D) F S 2 1 4. 3 1 6 125 1 3y 75 5 25 2 4 6 8 1 12 14 16 18 1 2. 1 2 1 12.12 2759.1 5.5.7944 1.75 2.518 2 14.316 1689.1 1475.7 1.1254.566 97.482 S68

mau 4 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14116\FJ586RB199.D) 2 S 3 2 rac - 5a 1 7. 2 7 2 3 2. 2 3 1 5 1 15 2 25 3 35 1 17.272 22988.8 256.4 1.2686.312 5.433 2 32.23 22594.1 2.8 1.712.693 49.567 mau 4 3 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\1413\586B-AS.D) 2 S 3. 9 5 2 5a 1 5 1 15 2 25 3 1 7. 7 3 7 1 17.737 26.7 3.5.7274.882.668 2 3.95 3751.5 312.8 1.518.651 99.332 S7

mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\1413\59RC.D) 12 1 8 6 4 2 S rac -5b 1 9. 1 8 7 3 3. 7 6 6 2 5 1 15 2 25 3 35 1 19.187 25834.1 773.5.5567.56 51.26 2 33.766 24795.1 464.8.816.594 48.974 mau 12 1 8 6 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\1413\59C.D) 2 S 5b 1 9. 9 2 4 2 5 1 15 2 25 3 35 3 4. 1 6 3 1 19.92 32738.4 923.9.5313.446 99.149 2 34.163 281.1 5.5.697.916.851 S72

mau 25 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14112\FJ595RA.D) 2 S 2 15 1 rac - 5c 4 8. 9 4 7 5 7. 7 3 6 5 1 2 3 4 5 6 mau 35 3 1 48.947 7856.2 11 1.98.688 51.49 2 57.736 7533.3 91 1.2617.694 48.951 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14112\FJ595A.D) 2 S 25 2 5c 5 8. 1 8 5 15 1 5 1 2 3 4 5 6 4 9. 9 7 7 1 49.977 423.6 6 1.1784.989 2.165 2 58.185 19137.9 216.3 1.3439.68 97.835 S74

mau 8 6 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14112\FJ595RB.D) 2 S 1 4. 3 1 1 4 2 F rac - 5d 2 2. 6 3 2 5 1 15 2 25 3 1 14.311 28313.7 641.3.6476.423 5.63 2 22.632 28242.1 324.6 1.261.441 49.937 mau 8 6 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14112\FJ595B.D) 2 S 1 4. 2 6 7 4 2 F 5d 5 1 15 2 25 2 3. 5 5 8 1 14.267 27523.7 646.4.6263.422 99.7 2 23.558 258.3 2.9 1.61.687.93 S76

mau 25 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14115\FJ513RB191.D) 2 S 2 15 rac - 5e 4 5. 7 9 6 1 6 7. 7 9 5 1 2 3 4 5 6 7 1 45.796 9185.5 14 1.12.722 5.515 2 67.79 8998.4 95.5 1.4631.754 49.485 mau 7 6 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14115\FJ513B192.D) 2 S 6 6. 5 3 5 4 3 5e 2 1 1 2 3 4 5 6 7 4 5. 7 5 3 1 45.753 914 14.2.9319.844 1.428 2 66.53 6316.6 66.3 1.5666.484 98.572 S78

mau 6 VWD1 A, 波长 =24 nm (D:\CHEM32\1\DATA\FEIJIE\15131\FJ5145R134.D) 5 4 3 2 1 4. 1 4 3 1 7. 3 7 4 1 2 4 6 8 1 12 14 16 18 1 14.143 829.8 23.6.512 1.58 5.646 2 17.374 88.6 23.6.583 1.171 49.354 mau VWD1 A, 波长 =24 nm (D:\CHEM32\1\DATA\FEIJIE\15131\FJ5171B-4135.D) 7 6 5 1 7.2 4 3 2 1 1 4. 1 4 4 2 4 6 8 1 12 14 16 18 1 14.144 1513.6 51.9.4861.99 7.986 2 17.2 17439.4 468.6.5419.931 92.14 S8

mau VWD1 A, 波长 =254 nm (D:\CHEM32\1\DATA\FEIJIE\15328\QQQ161B3.D) 25 2 15 2 5. 1 8 3 2. 8 4 7 1 5 5 1 15 2 25 3 1 25.18 11191.2 199.5.8539.434 51.485 2 32.847 1545.6 159 1.32.725 48.515 mau VWD1 A, 波长 =254 nm (D:\CHEM32\1\DATA\FEIJIE\15328\QQQ16B2.D) 2 175 15 125 1 75 H 8b 2 5. 1 4 1 5 25 3 3. 5 8 5 1 15 2 25 3 1 25.141 9846.5 113.5 1.3438.567 93.927 2 33.58 636.6 8.6 1.735.897 6.73 S82

mau 12 VWD1 A, 波长 =254 nm (D:\CHEM32\1\DATA\FEIJIE\15328\QQQ161A8.D) 1 8 6 1 7. 9 5 1 2 1. 8 6 7 2 9. 4 4 9 4 5. 3 2 2 4 2 1 2 3 4 5 1 17.951 6253.2 73.5 1.4176 1.373 27.393 2 21.867 591.6 74.9 1.3146 1.342 25.892 3 29.449 5458.7 81.2 1.122 1.9 23.912 4 45.322 525.4 61.2 1.4174.759 22.83 mau 175 15 VWD1 A, 波长 =254 nm (D:\CHEM32\1\DATA\FEIJIE\15328\QQQ16A7.D) 125 1 H 4 5.4 5 1 75 8c 5 25 2 9.1 8 7 1 2 3 4 5 1 29.187 424.9 6.7 1.639.851 4.687 2 45.451 8641.1 96.3 1.2671.746 95.313 S84

mau 1 VWD1 A, 波长 =22 nm (D:\CHEM32\1\DATA\FEIJIE\1521\FJ5185RA-255.D) 1 2. 1 2 6 8 2 3. 4 3 1 6 4 2 1 3. 1 5 7 1 4. 1 3 9 5 1 15 2 25 1 12.126 34747.9 95.9.662 2.31 45.958 2 13.157 2882.8 84.5125 1.154 3.813 3 14.139 2747.9 79.6.5119 1.111 3.634 4 23.431 35228.6 724.6.813 1.436 46.594 mau VWD1 A, 波长 =24 nm (D:\CHEM32\1\DATA\FEIJIE\1521\FJ5185A56.D) 6 5 2 4. 4 7 4 4 3 2 1 1 3. 1 1 6 5 1 15 2 25 1 13.116 161.4 41.9.5926 1.26 6.697 2 24.474 2231.8 453.7.7164 1.479 93.33 S86

E: Crystallographic Information for Product 3p S87

Table 1. Crystal data and structure refinement for 3p. Identification code cd214681 Empirical formula C16H 15 N 4 S 2 Formula weight 349.41 Temperature 293(2) K Wavelength.7173 Å Crystal system rthorhombic Space group P 21 21 21 Unit cell dimensions a = 7.7629(6) Å a= 9. b = 1.2271(8) Å b= 9. c = 2.6268(16) Å g = 9. Volume 1637.6(2) Å3 Z 4 Density (calculated) 1.417 Mg/m 3 Absorption coefficient.344 mm-1 F() 728 Crystal size.211 x.165 x.123 mm 3 Theta range for data collection 1.975 to 25.999. Index ranges -9<=h<=9, -12<=k<=12, -25<=l<=17 Reflections collected 9915 Independent reflections 3218 [R(int) =.27] Completeness to theta = 25.242 99.9 % Absorption correction Semi-empirical from equivalents Max. and. transmission.7457 and.6449 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 3218 / / 212 Goodness-of-fit on F2 1.24 Final R indices [I>2sigma(I)] R1 =.49, wr2 =.1339 R indices (all data) R1 =.565, wr2 =.146 Absolute structure parameter.(4) Extinction coefficient n/a Largest diff. peak and hole.45 and -.295 e.å -3 S9

Table 2. Atomic coordinates ( x 14) and equivalent isotropic displacement parameters (Å 2 x 1 3 ) for 3p. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. x y z U(eq) S(1) 953(3) 794(2) 4612(1) 1(1) S(2) 721(1) 9217(1) 1472(1) 54(1) N(1) 5543(4) 9113(4) 215(2) 45(1) (1) 3527(4) 12143(3) 229(1) 56(1) (2) 6566(4) 1181(3) 19(2) 7(1) (3) 8646(4) 9224(4) 1779(2) 78(1) (4) 6944(4) 7841(3) 1119(1) 62(1) C(1) -68(6) 84(5) 412(2) 67(1) C(2) -59(6) 8573(5) 359(3) 74(1) C(3) 2436(7) 8439(6) 471(2) 76(2) C(4) 1728(5) 8794(4) 355(2) 51(1) C(5) 2729(5) 9318(4) 2932(2) 47(1) C(6) 1986(6) 1624(4) 2687(2) 55(1) C(7) 2878(5) 1173(4) 283(2) 46(1) C(8) 2941(5) 112(3) 1542(2) 47(1) C(9) 3757(4) 8814(4) 1784(2) 42(1) C(1) 2777(5) 8316(4) 2379(2) 45(1) C(11) 3784(5) 7789(4) 1244(2) 49(1) C(12) 5288(6) 7369(4) 953(2) 56(1) C(13) 5283(9) 639(5) 482(2) 76(2) C(14) 3753(11) 5859(5) 293(2) 93(2) C(15) 2249(9) 6275(5) 558(2) 84(2) C(16) 2244(7) 7245(4) 132(2) 66(1) S91

Table 3. Bond lengths [Å] and angles [ ] for 3p. S(1)-C(1) 1.63(5) S(1)-C(3) 1.693(5) S(2)-(3) 1.412(3) S(2)-(2) 1.417(3) S(2)-(4) 1.585(3) S(2)-N(1) 1.67(3) N(1)-C(9) 1.497(5) N(1)-H(1A).74(4) (1)-C(7) 1.21(5) (4)-C(12) 1.415(6) C(1)-C(2) 1.456(7) C(1)-H(1).93 C(2)-C(4) 1.46(6) C(2)-H(2).93 C(3)-C(4) 1.341(6) C(3)-H(3).93 C(4)-C(5) 1.512(5) C(5)-C(1) 1.535(5) C(5)-C(6) 1.54(6) C(5)-H(5).98 C(6)-C(7) 1.497(5) C(6)-H(6A).97 C(6)-H(6B).97 C(7)-C(8) 1.494(5) C(8)-C(9) 1.545(5) C(8)-H(8A).97 C(8)-H(8B).97 C(9)-C(11) 1.529(5) C(9)-C(1) 1.531(5) C(1)-H(1A).97 C(1)-H(1B).97 C(11)-C(12) 1.381(6) C(11)-C(16) 1.389(6) C(12)-C(13) 1.395(6) C(13)-C(14) 1.362(9) C(13)-H(13).93 S92

C(14)-C(15) 1.357(9) C(14)-H(14).93 C(15)-C(16) 1.394(7) C(15)-H(15).93 C(16)-H(16).93 C(1)-S(1)-C(3) 95.2(2) (3)-S(2)-(2) 121.4(2) (3)-S(2)-(4) 14.1(2) (2)-S(2)-(4) 17.42(18) (3)-S(2)-N(1) 18.99(19) (2)-S(2)-N(1) 19.74(19) (4)-S(2)-N(1) 13.54(18) C(9)-N(1)-S(2) 116.9(2) C(9)-N(1)-H(1A) 18(3) S(2)-N(1)-H(1A) 18(3) C(12)-(4)-S(2) 116.6(2) C(2)-C(1)-S(1) 18.3(3) C(2)-C(1)-H(1) 125.9 S(1)-C(1)-H(1) 125.9 C(4)-C(2)-C(1) 113.1(5) C(4)-C(2)-H(2) 123.4 C(1)-C(2)-H(2) 123.4 C(4)-C(3)-S(1) 112.5(4) C(4)-C(3)-H(3) 123.7 S(1)-C(3)-H(3) 123.7 C(3)-C(4)-C(2) 11.8(4) C(3)-C(4)-C(5) 124.5(4) C(2)-C(4)-C(5) 124.7(4) C(4)-C(5)-C(1) 11.9(3) C(4)-C(5)-C(6) 111.8(3) C(1)-C(5)-C(6) 11.1(3) C(4)-C(5)-H(5) 17.9 C(1)-C(5)-H(5) 17.9 C(6)-C(5)-H(5) 17.9 C(7)-C(6)-C(5) 111.5(3) C(7)-C(6)-H(6A) 19.3 C(5)-C(6)-H(6A) 19.3 S93

C(7)-C(6)-H(6B) 19.3 C(5)-C(6)-H(6B) 19.3 H(6A)-C(6)-H(6B) 18. (1)-C(7)-C(8) 121.3(3) (1)-C(7)-C(6) 123.1(3) C(8)-C(7)-C(6) 115.6(3) C(7)-C(8)-C(9) 19.8(3) C(7)-C(8)-H(8A) 19.7 C(9)-C(8)-H(8A) 19.7 C(7)-C(8)-H(8B) 19.7 C(9)-C(8)-H(8B) 19.7 H(8A)-C(8)-H(8B) 18.2 N(1)-C(9)-C(11) 111.(3) N(1)-C(9)-C(1) 15.9(3) C(11)-C(9)-C(1) 111.2(3) N(1)-C(9)-C(8) 18.(3) C(11)-C(9)-C(8) 11.8(3) C(1)-C(9)-C(8) 19.8(3) C(9)-C(1)-C(5) 112.7(3) C(9)-C(1)-H(1A) 19.1 C(5)-C(1)-H(1A) 19.1 C(9)-C(1)-H(1B) 19.1 C(5)-C(1)-H(1B) 19.1 H(1A)-C(1)-H(1B) 17.8 C(12)-C(11)-C(16) 117.8(4) C(12)-C(11)-C(9) 122.8(4) C(16)-C(11)-C(9) 119.5(4) C(11)-C(12)-C(13) 121.5(4) C(11)-C(12)-(4) 123.8(3) C(13)-C(12)-(4) 114.6(4) C(14)-C(13)-C(12) 119.2(5) C(14)-C(13)-H(13) 12.4 C(12)-C(13)-H(13) 12.4 C(15)-C(14)-C(13) 12.7(4) C(15)-C(14)-H(14) 119.7 C(13)-C(14)-H(14) 119.7 C(14)-C(15)-C(16) 12.5(5) C(14)-C(15)-H(15) 119.8 S94

C(16)-C(15)-H(15) 119.8 C(11)-C(16)-C(15) 12.3(5) C(11)-C(16)-H(16) 119.9 C(15)-C(16)-H(16) 119.9 Symmetry transformations used to generate equivalent atoms: S95

Table 4. Anisotropic displacement parameters (Å2x 13) for 3p. The anisotropic displacement factor exponent takes the form: -2p 2 [ h 2 a* 2 U 11 +... + 2 h k a* b* U12 ] U 11 U 22 U 33 U 23 U 13 U 12 S(1) 126(1) 98(1) 75(1) 22(1) 15(1) -5(1) S(2) 44(1) 62(1) 58(1) 3(1) 9(1) -1(1) N(1) 37(2) 53(2) 46(2) 2(2) -2(1) 1(1) (1) 59(2) 46(1) 65(2) -2(1) -8(1) -6(1) (2) 71(2) 67(2) 73(2) 18(2) 24(2) 1(2) (3) 4(2) 11(3) 92(2) -1(2) 7(2) (2) (4) 62(2) 64(2) 61(2) -4(2) 11(2) 16(2) C(1) 52(2) 77(3) 7(3) -8(2) 21(2) -8(2) C(2) 58(3) 92(3) 71(3) 8(3) 11(3) -8(2) C(3) 67(3) 89(4) 72(3) 23(3) -7(2) -5(2) C(4) 52(2) 48(2) 52(2) -6(2) 2(2) -5(2) C(5) 4(2) 54(2) 47(2) -5(2) -2(2) -1(2) C(6) 58(2) 5(2) 58(2) -11(2) 4(2) -4(2) C(7) 38(2) 43(2) 57(2) -2(2) -7(2) -2(2) C(8) 44(2) 45(2) 53(2) 1(2) -7(2) -1(2) C(9) 38(2) 42(2) 46(2) (2) -4(2) -2(1) C(1) 41(2) 46(2) 48(2) -3(2) (2) -3(2) C(11) 64(2) 41(2) 42(2) (2) -8(2) -1(2) C(12) 79(3) 47(2) 43(2) 4(2) -4(2) 8(2) C(13) 117(5) 58(3) 52(2) -6(2) 3(3) 2(3) C(14) 17(6) 49(3) 59(3) -15(2) -36(4) 11(4) C(15) 119(5) 61(3) 71(3) -1(3) -35(3) -9(3) C(16) 84(3) 57(2) 56(2) -6(2) -23(2) -5(2) S96

Table 5. Hydrogen coordinates ( x 14) and isotropic displacement parameters (Å 2 x 1 3 ) for 3p. x y z U(eq) H(1) -1814 7817 4214 8 H(2) -772 8748 3157 88 H(3) 361 8481 4157 91 H(5) 3916 9475 374 56 H(6A) 766 152 26 66 H(6B) 2114 11284 321 66 H(8A) 3616 1452 1186 57 H(8B) 1784 9934 1385 57 H(1A) 332 752 2533 54 H(1B) 166 812 2253 54 H(13) 631 614 298 91 H(14) 374 524-2 111 H(15) 1213 599 421 11 H(16) 126 7529 128 79 H(1A) 58(5) 86(4) 2248(17) 34(11) S97