Supporting Information

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1 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

2 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, ; b) Wang, Y. Q.; Yu, C. B.; Wang, D. W.; Wang, X. B.; Zhou, Y.-G. rg. Lett. 28, 1, [2] a) K. Zumbansen, A. Döhring, B. List, Adv. Synth. Catal. 21, 352, ; b) J. E. Wilson, G. C. Fu, Angew. Chem. Int. Ed. 26, 45, [3] V. V. Mezheritskii, R. V. Tyurin, L. G. Minyaeva, A. N. Antonov, A. P. Zadorozhnaya, Russ. J. rg. Chem. 26, 42, S2

3 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 TCM MeCN THF full 96 5 Dioxane 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

4 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 TsH. H AcH 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 d 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

5 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) (m, 4H), (m, 4H), 6.96 (d, J = 8.4 Hz, 1H), 6. (s, 1H), (m, 1H), 3.5 (d, J = 14.4 Hz, 1H), (m, 2H), 2.7 (d, J = 8.8 Hz, 2H), (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 38.22, 43.93, 47.41, 52.29, 65.12, , 125.6, , 126.1, , , 128.9, 13.19, , , HRMS(EI) calcd for C 18 H 17 N 4 S [M] , found: ; 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 C; [α] 25 D = -3.3 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) (m, 6H), 7.2 (d, J = 8.4 Hz, 1H), 7.3 (d, J = 8.4 Hz, 1H), 5.7 (s, 1H), (m, 1H), 3.7 (d, J = 14.8 Hz, 1H), (m, 2H), (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, , , 126.1, 126.6, , 129., 13.27, 132.9, 14.69, , HRMS(EI) calcd for C 18 H 16 ClN 4 S [M] , found: ; 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

6 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), (m, 3H), (m, 1H), (m, 1H),7.7 (dd, J = 8., 1.2 Hz, 1H), 5.12 (s, 1H), (m, 1H), 3.1 (d, J = 14.8 Hz, 1H), (m, 1H), (m, 2H), (m, 1H), (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 37.94, 43.48, 47.21, 52.52, 65.1, , , , , 126.2, 126.6, , 13.38, 13.4, 13.51, , , HRMS(EI) calcd for C 18 H 16 BrN 5 S [M] , found: ; 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 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), (m, 3H), 7.15 (d, J = 8.4 Hz, 2H), 7.6 (d, J = 8.4 Hz, 2H), 5.35 (s, 1H), (m, 1H), 3.9 (d, J = 14.4 Hz, 1H), 2.92 (dd, J = 14., 1.6 Hz, 1H), (m, 1H), (m, 1H), (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, , 12.99, , , 126.2, 128.5, 13.32, , , , HRMS(EI) calcd for C 18 H 16 BrN 4 S [M] , found: ; 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 C; [α] 25 D = 1.4 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) (m, 2H), (m, 3H), (m, 1H), (m, 2H), 5.67 (s, 1H), (m, 1H), 3.7 (d, J = 14.8 Hz, 1H), (m, 1H), (m, 2H), (m, 1H), (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 33.74, 41.38, 45.98, 52.25, 65.2, , , , 124.6, , 125.1, , , , , , , , , 13.17, , , 162.3, HRMS(EI) calcd for C 18 H 16 FN 4 S [M] , found: ; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow S6

7 .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 C; [α] 25 D = 2.4 (c =.5 in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) (m, 2H), (m, 1H), (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), (m, 1H), 3.4 (d, J = 14.4 Hz, 1H), 2.88 (dd, J = 14.4, 2. Hz, 3H), (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, , , , , 126.1, , 13.16, , , , HRMS(EI) calcd for C 19 H 19 N 5 S [M] , found: ; 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 C; [α] 25 D = 29.4 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) (m, 2H), (m, 3H), (m, 1H), (m, 1H), 6.88 (d, J = 8. Hz, 1H), 5.18 (s, 1H), (m, 1H), 3.84 (s, 3H), (m, 2H), (m, 3H), (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, , 12.74, , , , , 128.2, , 13.7, , 157.3, HRMS(EI) calcd for C 19 H 19 N 5 S [M] , found: ; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 9.8 (major) and 13.9 (or). S7

8 3h, the product was obtained in 94% yield,.67 g, white solid. Mp C; [α] 25 D = 1.5 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) (m, 2H), (m, 1H), (m, 4H), 7.3 (dd, J = 8.4,.8 Hz, 1H), 5.56 (s, 1H), (m, 1H), 3.5 (d, J = 14. Hz, 1H), 2.88 (d, J = 14. Hz, 2H), (m, 2H), 2.31 (s, 3H), (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 21.1, 37.83, 44.2, 47.58, 52.24, 65.13, , , , , , , 13.14, , , , HRMS(EI) calcd for C 19 H 19 N 4 S [M] , found: ; 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 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), (m, 2H), (m, 1H), (m, 1H), 5.92 (s, 1H), (m, 1H), 3.12 (d, J = 14.8 Hz, 1H), 2.93 (d, J = 14. Hz, 2H), (m, 2H), (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 38.15, 43.22, 46.57, 51.92, 64.87, 11.98, , , , 126.9, , 129.9, 13.39, , , , HRMS(EI) calcd for C 19 H 16 N 2 4 S [M] , found: ; 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 C; [α] 25 D = -5.1 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) (m, 2H), (m, 1H), (m, 1H), (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

9 (m, 1H), 3.5 (d, J = 14.8 Hz, 1H), (m, 2H), (m, 1H), (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, , , 125.1, , 126.8, 13.14, , , , , HRMS(EI) calcd for C 19 H 17 N 6 S [M] , found: ; 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) (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), (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), (m, 1H), (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 36.6, 42.21, 46.47, 52.45, 65.2, , , , , 126.2, , , , , 13.19, 13.3, 13.8, , , HRMS(EI) calcd for C 2 H 19 N 4 S [M] , found: ; 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 C; [α] 25 D = 18.7 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) (m, 1H), (m, 2H), 7.3 (d, J = 8. Hz, 1H), 5.38 (s, 1H), (m, 2H), 2.66 (d, J = 14. Hz, 1H), (m, 1H), (m, 1H), (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, , , , , 13.1, , HRMS(EI) calcd for C 13 H 15 N 4 S [M] , found: ; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 11.8 (major) and 18.4 (or). S9

10 S 2 3m, the product was obtained in 64% yield,.36 g, pale yellow oil. [α] 25 D = (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), (m, 1H), (m, 1H), 7.32 (dd, J = 8.4, 1.2 Hz, 1H), 3.2 (d, J = 6.8 Hz, 2H), (m, 1H), 2.63 (dd, J = 18., 7.2 Hz, 1H), (m, 2H), (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, , 126.1, , , , , ; HRMS(EI) calcd for C 13 H 13 N 4 S [M] , found: ; 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 C; [α] 25 D = (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), (m, 1H), (m, 1H), 7.32 (dd, J = 8.4,.8 Hz, 1H), (m, 2H), (m, 2H), (m, 1H), (m, 2H), (m, 2H), (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, , 126.9, 128.4, , , , HRMS(EI) calcd for C 14 H 15 N 4 S [M] , found: ; 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), (m, 1H), (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), (m, 1H), (m, 4H), (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, , , 126.1, , , , , HRMS(EI) calcd for C 15 H 17 N 4 S [M] , found: S1

11 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 C; [α] 25 D = 6.2 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) (m, 1H), (m, 2H), (m, 1H), (m, 3H), 5.33 (s, 1H), (m, 1H), (m, 2H), (m, 2H), (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, , , , 126.1, , 126.4, 13.21, , , HRMS(EI) calcd for C 16 H 15 N 4 S 2 [M] , found: ; 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) (m, 4H), 7.6 (d, J = 8.4 Hz, 1H), (m, 1H), 6.9 (d, J = 3.2 Hz, 1H), 5.45 (s, 1H), (m, 1H), (m, 2H), (m, 2H), (m, 1H), (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, , , , 126.2, 13.22, , , , HRMS(EI) calcd for C 16 H 15 N 5 S [M] , found: ; 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 C; [α] 25 D = -2.4 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) (m, 3H), 7.67 (s, 1H), (m, 2H), 7.39 (dd, J = 8.4, 1.6 Hz, 1H), (m, 2H), (m, 2H), 7.3 (dd, J = 8., 1.2 Hz, 1H), 5.66 (s, S11

12 1H), (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), (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, , , 125.7, , , , , , , , , 13.21, , , , , HRMS(EI) calcd for C 22 H 19 N 4 S [M] , found: ; 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 C; [α] 25 D = 7.7 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) (m, 2H), (m, 3H), (m, 3H), (m, 1H), 3. (d, J = 14.4 Hz, 1H), 2.91 (d, J = 14.4 Hz, 2H), (m, 2H), (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 38.17, 43.7, 47.35, 51.93, 64.99, , 113.6, , , , , , , , , 127.3, , , , , 16.81, HRMS(EI) calcd for C 18 H 16 FN 4 S [M] , found: ; 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 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), (m, 1H), 3.24 (d, J = 14. Hz, 1H), 2.99 (d, J = 14. Hz, 1H), (m, 1H), 2.74 (t, J = 13.2 Hz, 1H) (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, , , , , , , , , , HRMS(EI) calcd for C 18 H 16 BrN 4 S [M] , found: ; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 4/1, flow.7 ml/, detection at 21nm) retention time = 8.4 (major) and 1.6 (or). S12

13 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) (m, 2H), (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), (m, 1H), 3.1 (d, J = 14.4 Hz, 1H), 2.86 (d, J = 13.6 Hz, 2H), (m, 2H), (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, , , , , , , , 15.48, 16.52, HRMS(EI) calcd for C 19 H 19 N 5 S [M] , found: ; 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 C; [α] 25 D = 24.3 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) (m, 2H), (m, 3H), (m, 2H), 6.93 (d, J = 8.4 Hz, 1H), 5.22 (s, 1H), (m, 1H), 3.7 (d, J = 14.4 Hz, 1H), (m, 1H), (m, 1H), (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, , , 126.3, , , , 13.79, , 142.2, , HRMS(EI) calcd for C 19 H 19 N 4 S [M] , found: ; 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 C; [α] 25 D = 33.1 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) (m, 7H), 6.99 (d, J = 8.4 Hz, 1H), 5.78 (s, 1H), (m, 1H), 3.2 (d, J = 14. Hz, 1H), 2.91 (d, J = 14. Hz, 2H), (m, 2H), (m, S13

14 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 38.16, 43.74, 47.35, 51.96, 64.98, 121.1, , , , , , 13.26, , , , HRMS(EI) calcd for C 18 H 16 ClN 4 S [M] , found: ; 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 C; [α] 25 D = -1.2 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) (m, 2H), 7.97 (d, J = 8. Hz, 1H), (m, 1H), (m, 1H), 7.37(d, J = 9.2 Hz, 1H), (m, 2H), (m, 1H), 2.47 (d, J = 14. Hz, 1H), 2.36 (d, J = 14.4 Hz, 1H ), (m, 1H), (m, 1H), (m, 2H), (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, , , , 129., , 13.7, , , , , HRMS(EI) calcd for C 18 H 17 N 4 S [M] , found: ; 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 C; [α] 25 D = 3.3 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) (m, 6H), (m, 1H), 6.78 (dd, J = 8.4, 2.4 Hz, 1H), 5.66, (s, 1H), (m, 1H), 3.3 (d, J = 14.4 Hz, 1H), (m, 2H), (m, 2H), (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, , 113.5, 121.7, 121.1, , , , , , 142., 15.41, 15.53, , , HRMS(EI) calcd for C 18 H 16 FN 4 S [M] , found: ; HPLC (DAICEL Chiralpak IA, hexane/ dichloromethane = 7/3, flow 1. ml/, detection at 24nm) retention time = 12. (or) and 14.3 (major). S14

15 2 S 5a, the product was obtained in 83% yield,.54 g, white solid. Mp 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), (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), (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), (m, 2H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 4.34, 44.39, 47.71, 51.29, 65.65, , , , , , , , , , , HRMS(EI) calcd for C 18 H 17 N 3 S [M] , found: ; 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 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), (m, 2H), (m, 1H), (m, 2H), (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, , , , 133.6, , , HRMS(EI) calcd for C 13 H 15 N 3 S [M] , found: ; 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 C; [α] 25 D = -9.5 (c = 1. in CH 2 Cl 2 ); 1 H-NMR (4 MHz, CDCl 3 ): δ (ppm) (m, 1H), (m, 2H), (m, 1H), (m, 2H), S15

16 (m, 2H), (m, 1H), (m, 2H), (m, 2H), (m, 1H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 24.66, 3.86, 35.79, 37.7, 41.15, 47.64, , , , 133.8, 134.2, 139.7, , HRMS(EI) calcd for C 14 H 15 N 3 S [M] , found: ; 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 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), (m, 1H), 7.54 (dd, J = 14., 7.6 Hz, 1H), (m, 1H), 7.5 (d, J = 7.6 Hz, 1H), 5.62 (s, 1H), (m, 1H), 3.8 (d, J = 14.8 Hz, 1H), (m, 3H), (m, 2H). 13 C-NMR (1 MHz, CDCl 3 ): δ (ppm) 39.87, 44.1, 47.41, 51.1, 65.5, , , 114.4, , , , 122.6, , 13.1, 13.4, 13.49, , 135.8, , , , , , HRMS(EI) calcd for C 18 H 16 FN 3 S [M] , found: ; 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) (m, 1H), (m, 2H), (m, 1H), (m, 2H), (m, 1H), (m, 4H), (m, 3H), (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, , , , , , , , HRMS(EI) calcd for C 15 H 17 N 3 S [M] , found: ; HPLC (DAICEL Chiralpak AY, hexane/ EtH = 7/3, flow.7 ml/, detection at 21nm) retention time = 45.8 (or) and 66.5 (major). S16

17 8a, the product was obtained in 52% yield,.19 g, colorless oil. [α] 25 D = (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), (m, 2H), (m, 3H), (m, 1H), (m, 1H), 4.99 (s, 1H), (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), (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, , , 12.92, , , , , , , , , , , , , 153.5, HRMS(EI) calcd for C 25 H 22 3 [M] , found: ; 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 = (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), (m, 1H), (m, 3H), 6.99 (d, J = 6.8 Hz, 1H), 6.88 (d, J = 7.2 Hz, 1H), 4.99 (s, 1H), (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), (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, , , 12.93, , , 124.5, , 127.1, 127.6, , , 138.1, , , , , HRMS(EI) calcd for C 26 H 24 3 [M] , found: ; HPLC (DAICEL Chiralpak IC, hexane/dcm = 1/1, flow 1. ml/, detection at 254nm) retention time = 25.1 (major) and 33.1 (or). S17

18 8c, the product was obtained in 6% yield,.25 g, colorless oil. [α] 25 D = (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), (m, 4H), 7.74 (d, J = 9.2 Hz, 1H), 7.56 (d, J = 8.4 Hz, 2H), (m, 2H), (m, 1H), 6.9 (dd, J = 7.6, 6.8 Hz, 1H), 5.6 (s, 1H), (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), (m, 1H), 2.34 (d, J = 13.2 Hz, 1H), 2.4(s, 3H), (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, , , 12.96, , , 125.2, , , , , , , , , 132.4, , , , , , HRMS(EI) calcd for C 29 H 24 3 [M] , found: ; 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 C; [α] 25 D = (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), (m, 1H), (m, 2H), 7.18 (d, J = 5.2 Hz, 1H), 6.91 (d, J = 7.2 Hz, 1H), 4.97 (s, 1H), (m, 1H), 3.29 (d, J = 12.8 Hz, 1H), 2.84 (t, J = 13.2 Hz, 1H), (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, , 12.44, 12.91, , , 125.1, 126.7, 127.2, , , , , , HRMS(EI) calcd for C 23 H 2 3 S [M] , found: ; HPLC (DAICEL Chiralpak IA, hexane/ DCM = 1/2, flow.8 ml/, detection at 254nm) retention time = 13.1 (or) and 24.5 (major). S18

19 D: NMR Spectra and HPLC chromatograms of Products S19

20 mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14927\FJ54RA-AY.D) mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\1417\FJ553D9.D) S2

21 S21

22 mau 12 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14116\GTT178F.D) S Cl rac - 3b mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14116\FJ-565A.D) S22

23 S23

24 mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14119\FJ573RA59.D) S Br rac - 3c mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14119\FJ573A6.D) S Br 3c S24

25 S25

26 mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14116\FJ565RB.D) 8 S Br rac - 3d mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14116\FJ565B-2.D) S Br 3d S26

27 S27

28 mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14116\FJ565RC.D) S F rac - 3e mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14116\FJ565C.D) S F 3e S28

29 S29

30 mau 4 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14118\FJ569RB-AS5.D) S rac - 3f mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14118\FJ569B-AS51.D) S f S3

31 S31

32 mau 8 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14119\FJ573RC62.D) S Me rac - 3g mau 2 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14119\FJ573C63.D) S Me 3g S32

33 S33

34 mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14118\FJ569RD46.D) 4 3 S rac - 3h mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14118\FJ569D47.D) S h S34

35 S35

36 mau 25 2 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ576RC-2112.D) S NC rac - 3i mau 4 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ576C113.D) S NC 3i S36

37 S37

38 mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14128\FJ573RB132.D) rac - 3j S mau 8 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14119\FJ573B-AS65.D) S j S38

39 S39

40 mau 12 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ576RB-217.D) S rac - 3k mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ576B18.D) S k S4

41 S41

42 mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\1413\59RA-AS.D) rac - 3l S mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\1413\59A-AS.D) S l S42

43 S43

44 mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14121\FJ574RB8.D) S 2 rac - 3m mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14121\FJ574B81.D) S 2 6 3m S44

45 S45

46 mau 4 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14121\FJ574RA78.D) S 2 3 rac - 3n mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14121\FJ574A79.D) 3n S S46

47 S47

48 mau 12 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14121\FJ574RC82.D) S rac - 3o mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14121\FJ574C83.D) S rac - 3o S48

49 S49

50 mau 4 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14127\FJ581RA-AS.D) S S rac - 3p mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14127\FJ581A.D) S S 3p S5

51 S51

52 mau 8 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ576RA-AS19.D) S rac - 3q mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ576A11.D) S q S52

53 S53

54 mau 12 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14118\FJ569RC44.D) S rac -3r mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14118\FJ569C45.D) S r S54

55 S55

56 mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ579RA114.D) F S rac - 3s mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ579A115.D) F S s S56

57 S57

58 mau 7 6 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ579RB-2121.D) Br S rac - 3t mau 2 15 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ579B-2123.D) Br S t S58

59 S59

60 mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ579RC117.D) Me S rac - 3u mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14124\FJ579C118.D) Me S u S6

61 S61

62 mau 4 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14127\FJ581RB-AS.D) S rac - 3v mau 8 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14127\FJ581B.D) S v S62

63 S63

64 mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14113\FJ596RB.D) Cl S rac - 3w mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14113\FJ596B.D) Cl S w S64

65 S65

66 mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14128\FJ583RC13.D) 12 1 S rac - 3x mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14128\FJ583C131.D) S 2 6 3x S66

67 S67

68 mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14114\FJ511RA17.D) F S rac - 3y mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14114\FJ511A.D) F S y S68

69 S69

70 mau 4 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14116\FJ586RB199.D) 2 S 3 2 rac - 5a mau 4 3 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\1413\586B-AS.D) 2 S a S7

71 S71

72 mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\1413\59RC.D) S rac -5b mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\1413\59C.D) 2 S 5b S72

73 S73

74 mau 25 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14112\FJ595RA.D) 2 S rac - 5c mau VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14112\FJ595A.D) 2 S c S74

75 S75

76 mau 8 6 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14112\FJ595RB.D) 2 S F rac - 5d mau 8 6 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14112\FJ595B.D) 2 S F 5d S76

77 S77

78 mau 25 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14115\FJ513RB191.D) 2 S 2 15 rac - 5e mau 7 6 VWD1 A, 波长 =21 nm (D:\CHEM32\1\DATA\FEIJIE\14115\FJ513B192.D) 2 S e S78

79 S79

80 mau 6 VWD1 A, 波长 =24 nm (D:\CHEM32\1\DATA\FEIJIE\15131\FJ5145R134.D) mau VWD1 A, 波长 =24 nm (D:\CHEM32\1\DATA\FEIJIE\15131\FJ5171B-4135.D) S8

81 S81

82 mau VWD1 A, 波长 =254 nm (D:\CHEM32\1\DATA\FEIJIE\15328\QQQ161B3.D) mau VWD1 A, 波长 =254 nm (D:\CHEM32\1\DATA\FEIJIE\15328\QQQ16B2.D) H 8b S82

83 S83

84 mau 12 VWD1 A, 波长 =254 nm (D:\CHEM32\1\DATA\FEIJIE\15328\QQQ161A8.D) mau VWD1 A, 波长 =254 nm (D:\CHEM32\1\DATA\FEIJIE\15328\QQQ16A7.D) H c S84

85 S85

86 mau 1 VWD1 A, 波长 =22 nm (D:\CHEM32\1\DATA\FEIJIE\1521\FJ5185RA-255.D) mau VWD1 A, 波长 =24 nm (D:\CHEM32\1\DATA\FEIJIE\1521\FJ5185A56.D) S86

87 E: Crystallographic Information for Product 3p S87

88 S88

89 S89

90 Table 1. Crystal data and structure refinement for 3p. Identification code cd Empirical formula C16H 15 N 4 S 2 Formula weight Temperature 293(2) K Wavelength.7173 Å Crystal system rthorhombic Space group P Unit cell dimensions a = (6) Å a= 9. b = (8) Å b= 9. c = (16) Å g = 9. Volume (2) Å3 Z 4 Density (calculated) Mg/m 3 Absorption coefficient.344 mm-1 F() 728 Crystal size.211 x.165 x.123 mm 3 Theta range for data collection to Index ranges -9<=h<=9, -12<=k<=12, -25<=l<=17 Reflections collected 9915 Independent reflections 3218 [R(int) =.27] Completeness to theta = % 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 F 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 e.å -3 S9

91 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

92 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

93 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) S(1)-C(1)-H(1) C(4)-C(2)-C(1) 113.1(5) C(4)-C(2)-H(2) C(1)-C(2)-H(2) C(4)-C(3)-S(1) 112.5(4) C(4)-C(3)-H(3) S(1)-C(3)-H(3) 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

94 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) C(13)-C(14)-H(14) C(14)-C(15)-C(16) 12.5(5) C(14)-C(15)-H(15) S94

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

96 Table 4. Anisotropic displacement parameters (Å2x 13) for 3p. The anisotropic displacement factor exponent takes the form: -2p 2 [ h 2 a* 2 U 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

97 Table 5. Hydrogen coordinates ( x 14) and isotropic displacement parameters (Å 2 x 1 3 ) for 3p. x y z U(eq) H(1) H(2) H(3) H(5) H(6A) H(6B) H(8A) H(8B) H(1A) H(1B) H(13) H(14) H(15) H(16) H(1A) 58(5) 86(4) 2248(17) 34(11) S97