Tributylphosphine-Catalyzed Cycloaddition of Aziridines with Carbon Disulfide and Isothiocyanate

upporting Information Tributylphosphine-Catalyzed Cycloaddition of Aziridines with Carbon Disulfide and Isothiocyanate Jing-Yu Wu, Zhi-Bin Luo, Li-Xin Dai and Xue-Long Hou* a tate Key Laboratory of Organometallic Chemistry, b hanghai-hong Kong Joint tate Key Laboratory of Organometallic Chemistry hanghai Institute of Organic Chemistry, Chinese Academy of ciences, 354 Fenglin Road, hanghai 200032, China E-mail: xlhou@mail.sioc.ac.cn Table of contents: General ------------------------------------------------------------------------------------------ -2 General procedure for the reaction of N-Ts aziridine with carbon disulfide ----------- -2 General procedure for the reaction of N-Ts aziridine with isothiocyanate ------------- -5 References for upporting Information ----------------------------------------------------- -11 1 H/ 13 C NMR spectra---------------------------------------------------------------------------- -12-1

General Acetonitrile and t-buoh were freshly distilled from CaH 2 and magnesium and iodine. PhNC and C 2 were distilled freshly before use. Tributylphosphine was purchased and used directly. All reactions were carried out under argon atmosphere using oven-dried and/or flame dried glassware. Flash column chromatography was carried out using ilica gel 60 (0.035-0.070 mm particle size). Proton (300 MHz) and carbon (75 MHz) NMR spectra were recorded using an internal deuterium lock. All samples were recorded in CDCl 3. Mechanistic study was achieved in C 6 D 6. Chemical shifts are quoted in parts per million and referenced to CHCl 3 (7.27 for 1 H-NMR and 77.0 for 13 C-NMR spectroscopy). Infra-red spectra were recorded on an FT-IR spectrometer. N-Ts Aziridines 1a-k, 1m-n were prepared using the literature procedures. 1 N-Ts Aziridines 1l was prepared using the literature procedures. 2 Experimental procedures and characterization data General procedure: cycloaddition of N-Ts aziridine with carbon disulfide In a chlenk tube equipped with condenser, Bu 3 P (6.25 μl, 0.025 mmol) was added to a stirring, r.t. mixture of aziridine (0.25 mmol), carbon disulfide (60 μl, 1 mmol) and anhydrous t-buoh (2 ml) under argon. Then heat the mixture to reflux for 10 hours until aziridine was disappeared from TLC. After then, the mixture was concentrated and the residue was purified by flash chromatography on silica gel using PE/EtOAc (10:1) as eluent to give 2. trans-n-tosyl-4,5-cyclohexa[d]thiazole-2-thione (2a) Ts N Yield: 92%. yellow solid. mp 181-182. 1 H-NMR (CDCl 3, 300 MHz): δ 1.25-1.26 (m, 3H), 1.86-2.02 (m, 4H), 2.43 (s, 3H), 3.18 (m, 1H), 3.58 (ddd, J = 3.3 Hz, 11.7 Hz, 11.7 Hz, 1H), 4.05 (ddd, J = 3.3 Hz, 11.1 Hz, 11.4 Hz, 1H), 7.30 (d, J = 7.8 Hz, 2H), 7.86 (d, J = 8.4 Hz, 2H). 13 C-NMR (CDCl 3, 75 MHz): δ 21.7, 24.3, 25.0, 28.6, 33.0, 51.8, 77.1, 128.7, 129.3, 134.6, 145.3, 200.5. IR (KBr pellet): 2941, 1594, 1373, 1204, 1170, 1074 cm -1. EI-M m/z: 328 (M+1). Anal. Calcd for C 14 H 17 NO 2 3 : C 51.35, H 5.23, N 4.28. Found: C 51.58, H 5.09, N 4.18. trans-n-tosyl-4,5-cyclohepta [d]thiazole-2-thione (2c) -2

Ts N Yield: 41%. yellow solid. mp 181-182. 1 H-NMR (CDCl 3, 300 MHz): δ 1.60-2.05 (m, 9H), 2.44 (s, 3H), 3.93 (ddd, J = 3.6 Hz, 9.6 Hz, 9.6 Hz, 1H), 4.77 (ddd, J = 3.9 Hz, 9.9 Hz, 9.9 Hz, 1H), 4.77(m, 1H), 7.30 (d, J = 8.1 Hz, 2H), 7.86 (d, J = 8.4 Hz, 2H). 13 C-NMR (CDCl 3, 75 MHz): δ 21.7, 24.5, 25.6, 27.2, 31.6, 35.7, 48.6, 75.9, 128.9, 129.2, 134.8, 145.2, 199.7. IR (KBr pellet): 2930, 1594, 1455, 1378, 1360, 1227, 1176, 1086 cm -1. EI-M m/z: 342 (M+1). Anal. Calcd for C 15 H 19 NO 2 3 : C 52.75, H 5.61, N 4.10. Found: C 52.75, H 5.56, N 4.01. 4-Butyl-N-tosylthiazolidine-2-thione (2e) Ts N Yield: 98%. yellow solid. mp 72-74. 1 H-NMR (CDCl 3, 300 MHz): δ 0.93-0.98 (t, J = 6.3 Hz, 3H), 1.40-1.47 (m, 4H), 1.95-2.24 (m, 2H), 2.44 (s, 3H), 3.00(d, J = 11.1 Hz, 1H), 3.68 (dd, J = 7.5 Hz, 7.8 Hz, 1H), 5.24 (m, 1H), 7.31 (d, J = 7.5 Hz, 2H), 7.91 (d, J = 6.6 Hz, 2H). 13 C-NMR (CDCl 3, 75 MHz): δ 13.9, 21.7, 22.3, 27.7, 32.7, 33.7, 69.8, 129.2, 129.5, 134.4, 145.5, 197.0. IR (KBr pellet): 2956, 1597, 1457, 1365, 1230, 1169, 1066 cm -1. EI-M m/z: 330 (M+1). Anal. Calcd for C 14 H 19 NO 2 3 : C 51.03, H 5.81, N 4.25. Found: C 51.03, H 5.77, N 3.97. 4-Hexyl-N-tosylthiazolidine-2-thione (2f) Ts N Yield: 90%. yellow solid. mp 76-77. 1 H-NMR (CDCl 3, 300 MHz): δ 0.92 (t, J = 6.3 Hz, 3H), 1.26-1.48 (m, 8H), 2.00-2.17 (m, 2H), 2.44 (s, 3H), 3.02 (d, J = 11.1 Hz, 1H), 3.70 (dd, J = 7.5 Hz, 7.5 Hz, 1H), 5.23 (m, 1H), 7.32 (d, J = 8.4 Hz, 2H), 7.91 (d, J = 8.1 Hz, 2H). 13 C-NMR (CDCl 3, 75 MHz): δ 14.0, 21.7, 22.5, 25.6, 28.8, 31.5, 33.0, 33.7, 69.8, 129.2, 129.4, 134.4, 145.5, 197.0. IR (KBr pellet): 2927, 1597, 1469, 1366, 1230, 1170, 1091 cm -1. EI-M m/z: 358 (M+1). Anal. Calcd for C 16 H 23 NO 2 3 : C 53.75, H 6.48, N 3.92. Found: C 53.62, H 6.48, N 3.92. 4-Hexadecyl-N-tosylthiazolidine-2-thione (2g) -3

Ts N Yield: 83%. yellow solid. mp 70-71. 1 H-NMR (CDCl 3, 300 MHz): δ 0.86 (t, J = 7.5 Hz, 3H), 1.20-1.49 (m, 28H), 2.00-2.12 (m, 2H), 2.45 (s, 3H), 3.00 (d, J = 11.4 Hz, 1H), 3.67 (dd, J = 7.5 Hz, 7.5 Hz, 1H), 5.21 (m, 1H), 7.30 (d, J = 8.7 Hz, 2H), 7.90 (d, J = 8.7 Hz, 2H). 13 C-NMR (CDCl 3, 75 MHz): δ 14.1, 21.7, 22.6, 25.7, 29.1, 29.3, 29.4, 29.5, 29.6, 29.59, 29.62, 29.64, 31.86, 32.96, 33.7, 69.8, 129.2, 129.5, 134.4, 145.5, 197.0. IR (KBr pellet): 2918, 2850, 1595, 1468, 1358, 1232, 1172, 1066 cm -1. EI- M m/z: 496 (M-1). Anal. Calcd for C 26 H 43 NO 2 3 : C 62.73, H 8.71, N 2.81. Found: C 62.97, H 8.94, N 2.72. 4-Benzyl-N-tosylthiazolidine-2-thione (2h) Ts N Yield: 93%. yellow solid. mp 86-87. 1 H-NMR (CDCl 3, 300 MHz): δ 2.45 (s, 3H), 2.96 (d, J = 11.4 Hz, 1H), 3.28 (m, 1H), 3.50 (m, 2H), 5.42 (m, 1H), 7.30-7.40 (m, 7H), 7.97 (d, J = 8.7 Hz, 2H). 13 C- NMR (CDCl 3, 75 MHz) δ: 21.7, 32.7, 38.5, 70.4, 127.4, 129.0, 129.32, 129.36, 129.5, 134.4, 135.8, 145.7, 196.8. IR (KBr pellet): 1593, 1454, 1369, 1236, 1172, 1065, 984 cm -1. EI-M m/z: 91 (PhCH 2 + ). Anal. Calcd for C 17 H 17 NO 2 3 : C 56.17, H 4.71, N 3.85. Found: C 56.19, H 5.02, N 3.60. 4-Methyl-4-propyl-N-tosylthiazolidine-2-thione (2i) Ts N Yield: 91%. yellow liquid. 1 H-NMR (CDCl 3, 300 MHz): δ 1.04 (t, J = 7.5 Hz, 3H), 1.52-1.59 (m, 2H), 1.95-2.24 (m, 2H), 1.97 (s, 3H), 2.08-2.11 (m, 1H), 2.39-2.46 (m, 1H), 2.43 (s, 3H), 3.21(d, J = 11.4 Hz, 1H), 3.37 (d, J = 11.4 Hz, 1H), 7.30 (d, J = 8.7 Hz, 2H), 7.88 (d, J = 6.9 Hz, 2H). 13 C-NMR (CDCl 3, 75 MHz): δ 14.2, 18.0, 21.6, 27.5, 41.0, 42.4, 81.7, 129.0, 129.4, 135.7, 145.0, 199.2. IR (KBr pellet): 2963, 1596, 1465, 1357, 1232, 1168, 1085 cm -1. EI-M m/z: 254 (M-C 2 +1). Anal. Calcd for C 14 H 19 NO 2 3 : C 51.03, H 5.81, N 4.25. Found: C 50.94, H 5.80, N 4.09. 4-Phenyl-N-tosylthiazolidine-2-thione (2j) and 5-phenyl-N-tosylthiazolidine-2-thione (2j ) -4

Ts N + 1 : 1 N Ts Yield: 98%. yellow solid. 1 H-NMR (CDCl 3, 300 MHz): δ 2.46 (s, 3H), 4.60 (m, 1H), 4.98 (m, 2H), 7.25-7.43 (m, 7H), 7.90 (d, J = 6.6 Hz, 2H). 13 C-NMR (CDCl 3, 75 MHz): δ 21.6, 21.8, 37.4, 48.6, 63.6, 71.6, 126.4, 127.31, 128.72, 128.94, 129.01, 129.07, 129.19, 129.21, 129.25, 129.41, 129.94, 133.42, 133.61, 136.33, 138.35, 145.49, 145.94, 197.1,197.9. IR (KBr pellet): 1594, 1074 cm -1. EI-M m/z: 350 (M+1). Anal. Calcd for C 16 H 15 NO 2 3 : C 54.99, H 4.33, N 4.01. Found: C 54.89, H 4.11, N 3.73. General procedure: cycloaddition of N-Ts aziridine with isothiocyanate In a chlenk tube equipped with condenser, n Bu 3 P (6.25 μl, 0.025 mmol) was added to a stirring, rt mixture of aziridine (0.25 mmol), isothiocyanate (60 μl, 0.5 mmol) and anhydrous acetonitrile (2 ml) under argon. Then heat the mixture to reflux for 24 hours. After then, the mixture was concentrated and the residue was purified by flash chromatography on silica gel using PE/EtOAc (10:1) as eluent to give 3. trans-n-(3-tosyl-4,5-cyclohexa[d]thiazolidin-2-ylidene)aniline (3a) Ts N NPh Yield: 78%. white solid. 1 H-NMR (300 MHz, CDCl 3 ): δ 1.35-1.57 (m, 3H), 1.68-1.86 (m, 2H), 1.93-2.03 (m, 2H), 2.45 (s, 3H), 3.13-3.26 (m, 2H), 3.62 (td, J = 3.3 Hz, 11.1 Hz, 1H), 6.55 (d, J = 0.9 Hz, 2H), 7.04 (t, J = 7.2 Hz, 1H), 7.12 (t, J = 10.2 Hz, 8.1 Hz, 2H), 7.31 (d, J = 8.1 Hz, 2H), 7.90 (d, J = 8.4 Hz, 2H). 13 C-NMR (75 MHz, CDCl 3 ): δ = 21.7, 24.4, 25.3, 29.4, 32.7, 49.1, 70.6, 120.5, 124.3, 128.9, 129.0, 129.1, 135.2, 144.5, 150.0 154.8. IR (KBr pellet): 1641, 1594, 1359, 1174, 1087 cm -1. M-EI m /z: 387.1 (M + H), 409.1 (M + Na), 441.2 (M + Na + MeOH). Anal.Calcd. for C 20 H 22 N 2 O 2 2 : C 62.15, H 5.74, N 7.25. Found: C 61.98, H 5.76, N 7.19. trans-n-(3-tosyl-4,5-cyclopenta[d]thiazolidin-2-ylidene)aniline (3b) -5

Ts N NPh Yield: 16%. white solid. 1 H-NMR (300 MHz, CDCl 3 ): δ 1.69-1.83 (m, 2H), 1.95-2.15 (m, 3H), 2.23-2.30 (m, 1H), 2.46 (s, 3H), 4.04 (t, J = 6Hz, 1H), 5.04 (dd, J = 13.2 Hz, 7.5Hz, 1H), 6.71 (d, J = 7.2Hz, 2H), 7.04 (t, J = 7.5Hz, 1H), 7.23 (t, J = 7.5Hz, 2H), 7.32 (d, 7.5Hz, 2H), 7.98 (d, J = 8.1Hz, 2H). 13 C- NMR (75 MHz, CDCl 3 ): δ 21.6, 23.2, 33.0, 33.9, 45.6, 66.3, 120.7, 123.9, 128.7, 128.9, 129.1, 135.7, 144.4, 150.1, 153.0. IR (KBr pellet): 1635, 1591, 1355, 1174 cm -1. M-EI m /z: 373.0 (M + H), 395.0 (M + Na), 427.0 (M + Na + MeOH). HRM (EI) Calcd. For C 19 H 21 N 2 O 2 2 +1 : 373.1039. Found: 373.1056. trans-n-(3-tosyl-4,5-cyclohepta[d]thiazolidin-2-ylidene)aniline (3c) Ts N NPh Yield: 47%. white solid. 1 H-NMR (300 MHz, CDCl 3 ): δ 1.62-1.83 (m,8h), 1.99-2.08 (m, 1H), 2.45 (s, 3H), 3.02-3.09 (m, 1H), 3.54 (td, J = 10.5Hz, 3.9Hz, 1H), 4.24 (td, J = 9.3Hz, 3.9Hz, 1H), 6.47 (d, J = 7.2Hz, 2H), 7.03 (t, J = 7.2Hz, 7.8Hz, 1H), 7.19 (t, J = 7.8Hz, 2H), 7.30 (d, J = 8.1Hz, 2H), 7.88 (d, J = 8.1Hz, 2H). 13 C-NMR (75 MHz, CDCl 3 ): δ 21.6, 25.0, 25.6, 27.3, 32.4, 36.0, 47.3, 68.7, 120.5, 124.2, 128.8, 129.1, 135.7, 144.4, 150.1, 154.8. IR (KBr pellet): 1641, 1593, 1343, 1169, 1155 cm -1. M-EI (m/z): 401.1 (M + H), 423.1 (M + Na), 455.1 (M + Na + MeOH). Calcd. for C 21 H 24 N 2 O 2 2 : C, 62.97 H, 6.04 N, 6.99. Found: C, 62.51 H, 6.05 N, 6.81. N-(4-Butyl-3-tosylthiazolidin-2-ylidene)aniline (3e) Ts N NPh Yield: 39%. white solid. 1 H-NMR (300 MHz, CDCl 3 ): δ 0.93 (t, J = 7.2Hz, 3H), 1.32-1.50 (m, 4H), 1.92 (dd, J = 7.2Hz, 6.0Hz, 2H), 2.43 (s, 3H), 2.88 (d, J = 10.1Hz, 1H), 3.31 (dd, J = 6.9 Hz, 11.4 Hz, 1H), 4.85 (dd, J = 7.5Hz, 6.9Hz, 1H), 6.69 (d, J = 1.5Hz, 2H), 7.03 (t, J = 6.3Hz, 4.5Hz, 1H), 7.23 (t, J = 7.5Hz, 2H), 7.31 (d, J = 8.1Hz, 2H), 7.96 (d, J = 8.4Hz, 2H). 13 C-NMR (75 MHz, CDCl 3 ): δ = 13.8, 21.5, 22.3, 27.9, 31.8, 33.2, 61.7, 120.6, 124.0, 128.7, 128.8, 129.0, 136.1, 144.4, 150.2, 152.5; IR (KBr -6

pellet): 1626, 1590, 1341, 1161, 1085 cm -1. M-EI (m/z): 389.2 (M + H), 411.2 (M + Na), 443.3 (M + Na + MeOH). Calcd. for C 20 H 24 N 2 O 2 2 : C, 61.82 H, 6.23 N, 7.21. Found: C, 61.84 H, 6.39 N, 7.10. N-(4-Hexyl-3-tosylthiazolidin-2-ylidene)aniline (3f) Ts N NPh Yield: 53%. white solid. 1 H-NMR (300 MHz, CDCl 3 ): δ 0.78-0.95 (m, 4H), 1.21-1.51 (m, 8H), 1.92 (dd, J = 6.9Hz, 13.5Hz, 2H), 2.43 (s, 3H), 2.88 (d, J = 10.1Hz, 1H), 3.31 (dd, J = 6.9Hz, 11.1Hz, 1H), 4.85 (dd, J = 6.9Hz, 13.8Hz), 6.69 (d, J = 2.4Hz, 2H), 7.03 (t, J = 7.5Hz, 1H), 7.23 (t, J = 7.8Hz, 2H), 7.30 (d, J = 8.1Hz, 2H), 7.96 (d, J = 8.4Hz, 2H). 13 C-NMR (75 MHz, CDCl 3 ): δ = 13.9, 21.5, 22.4, 25.8, 28.8, 31.5, 31.8, 33.5, 61.7, 120.5, 124.0, 128.7, 128.8, 129.0, 136.1, 144.3, 150.2, 152.4. IR (KBr pellet): 1631, 1592, 1367, 1173, 1082 cm -1. M-EI (m/z): 389.2 (M + H), 411.2 (M + Na), 443.3 (M + Na + MeOH). Calcd. for C 22 H 28 N 2 O 2 2 : C, 63.43 H, 6.77 N, 6.72. Found: C, 63.40 H, 6.85 N, 6.65. N-(4-Hexyl-3-tosylthiazolidin-2-ylidene)aniline (3g) Ts N NPh Yield: 53%. white solid. 1 H-NMR (300 MHz, CDCl 3 ): δ 0.87 (t, J = 7.2Hz, 3H), 1.27-1.36 (m, 28H), 1.90 (dd, J = 6.6Hz, 13.2Hz, 2H), 2.43 (s, 3H), 2.88 (d, J = 11.1Hz, 1H), 3.31 (dd, J = 7.2Hz, 11.1Hz, 1H), 4.85 (dd, J = 7.2Hz, 13.8Hz, 1H), 6.69 (d, J = 4.2Hz, 2H), 7.03 (t, J = 7.2Hz, 1H), 7.22 (t, J = 7.8Hz, 2H), 7.30 (d, J = 8.4Hz, 2H), 7.96 (d, J = 8.4Hz, 2H). 13 C-NMR (75 MHz, CDCl 3 ): δ 14.0, 21.5, 22.6, 25.9, 29.1, 29.2, 29.3, 29.4, 29.5, 29.6, 31.8, 33.5, 61.7, 120.6, 124.0, 128.7, 128.8, 129.0, 136.1, 144.3, 150.2, 152.4. IR (KBr pellet): 1635, 1593, 1341, 1160, 1087 cm -1. M-EI (m/z): 557.4 (M + H), 579.4 (M + Na). Calcd. for C 32 H 48 N 2 O 2 2 : C, 69.02 H, 8.69 N, 5.03. Found: C, 68.78 H, 8.54 N, 4.90. N-(4-Phenyl-3-tosylthiazolidin-2-ylidene)aniline (3j) and N-(5-phenyl-3-tosylthiazolidin-2- ylidene)aniline (3j') -7

Ts N 3j NPh N Ts 3j' NPh Yield: 78%. white solid. 1 H-NMR (300 MHz, CDCl 3 ): δ 2.48 (s, 3H), 4.05 (dd, J = 9Hz, 8.7Hz, 1H), 4.59 (dd, J = 6.0Hz, 10.5Hz, 1H), 4.79 (dd, J = 6.3Hz, 8.4Hz, 1H), 6.78 (dd, J = 1.2Hz, 8.4Hz, 2H), 7.98 (d, J = 8.1Hz, 2H), 7.04-7.17 (m, 2H), 7.23-7.37 (m, 12H), 3.03 (dd, J = 0.9Hz, 10.8Hz, 1H), 3.81 (dd, J = 7.2Hz, 10.5Hz, 1H), 5.94 (d, J = 6.9Hz, 1H), 6.86 (dd, J = 0.9Hz, 8.1Hz, 2H), 7.64 (d, J = 8.1Hz, 2H). 13 C-NMR (75 MHz, CDCl 3 ): δ 21.3, 21.4, 35.4, 46.5, 56.5, 63.3, 120.5, 120.6, 124.1, 126.0, 127.2, 128.2, 128.4, 128.7, 128.8, 129.0 129.1, 134.2, 135.1, 136.3, 139.2, 144.2, 144.7, 149.7, 149.9, 152.0, 152.6. IR (KBr pellet): 1646, 1591, 1354, 1168, 1098 cm -1. M-EI (m/z): 409.2 (M + H), 431.2 (M + Na), 463.2 (M + Na + MeOH). Calcd. for C 22 H 20 N 2 O 2 2 : C, 64.68 H, 4.93 N, 6.86. Found: C, 64.83 H, 5.13 N, 6.65. N-(5-Methyl-4-pentyl-3-tosylthiazolidin-2-ylidene)aniline (3k) and N-(4-methyl-5-pentyl-3- tosylthiazolidin-2-ylidene)aniline (3k ) (Compounds have four isomer) 3k Ts N NPh 3k' N Ts NPh Yield: 62%. pale yellow liquid. 1 H-NMR (300 MHz, CDCl 3 ): δ 0.79-0.92 (m, 6H), 1.96-1.89 (m. 20H), 2.43 (s, 3H), 2.46 (s, 2H), 2.64-2.76 (m, 2H), 3.89-3.98 (m, 1H), 4.72-4.79 (m, 1H), 6.71-6.76 (m, 1H), 7.02 (t, J = 7.2Hz, 1H), 7.20-7.25 (m, 5H), 7.82 (d, J = 5.4Hz, 2H), 7.94-8.01 (m, 1H). 13 C-NMR (75 MHz, CDCl 3 ): δ 11.76, 13.63, 13.72, 13.79, 13.85, 14.06, 20.80, 21.34, 21.43, 22.14, 22.20, 22.28, 23.68, 25.53, 26.09, 26.28, 26.52, 30.95, 31.04, 31.25, 34.22, 36.58, 39.96, 42.22, 44.98, 50.39, 56.52, 62.56, 68.96, 120.37, 120.60, 120.69, 123.78, 127.59, 128.59, 128.76, 128.79, 128.82, 129.01, 129.21, 129.34, 135.25, 135.74, 135.92, 144.01, 144.33, 144.37, 149.88, 150.03, 150.96, 151.60. M-EI (m/z): 417.3 (M + H). HRM (EI) Calcd. For C 22 H 29 N 2 O 2 +1 2 : 417.1665. Found: 417.1670. N-(5-Phenyl-2-methoxycarbonyl-3-tosylthiazolidin-2-ylidene)aniline (3l) -8

MeO 2 C Ts N NPh Yield: 38%. white solid. 1 H-NMR (300 MHz, CDCl 3 ): δ 2.44 (s, 3H), 3.28 (s, 3H), 5.28 (dd, J = 8.1Hz, 10.8Hz, 2H), 6.86 (d, J = 7.2Hz, 2H), 7.08 (t, J = 7.5Hz, 1H), 7.25-7.32 (m, 9H), 7.98 (d, J = 8.7Hz, 2H). 13 C-NMR (75 MHz, CDCl 3 ): δ = 21.7, 49.6, 52.1, 66.0, 120.8, 124.4, 128.3, 128.7, 128.8, 128.9, 129.2, 129.7, 132.4, 134.9, 144.9, 149.7, 151.0, 167.7. IR (KBr pellet): 1754, 1646, 1591, 1362, 1172, 1122 cm -1. M-EI (m/z): 467.1 (M + H), 489.1 (M + Na), 521.2 (M + Na + MeOH). HRM (EI) Calcd. For C 24 H 23 N 2 O 4 +1 2 : 467.1094. Found: 467.1089. N-(3-Tosyl-4,5-(2-cyclohexe)[d]thiazolidin-2-ylidene)aniline (3m) Ts N NPh Yield: 77%. white solid. 1 H-NMR (300 MHz, CDCl 3 ): δ 2.20 (t, J = 13.5Hz, 1H), 2.39-2.40 (m, 1H), 2.43 (s, 3H), 2.58 (t, J = 12.6Hz, 1H), 3.45 (td, J = 11.7Hz, 5.1Hz, 2H), 3.88 (td, J = 11.8Hz, 5.1Hz, 1H), 5.67-5.80 (m, 2H), 6.57 (d, J = 7.8Hz, 2H), 7.04 (t, J = 7.5Hz, 1H), 7.22 (t, J = 7.5Hz, 2H), 7.30 (d, J = 8.1Hz, 2H), 7.90 (d, J = 7.8Hz, 2H). 13 C-NMR (75 MHz, CDCl 3 ): δ 21.6, 30.3, 33.5, 44.9, 66.2, 120.4, 124.2, 124.3, 125.7, 128.9, 129.0, 129.1, 134.6, 144.7, 150.0, 154.6. IR (KBr pellet): 3030, 2907, 1632, 1592, 1367, 1174 cm -1. M-EI (m /z): 385.2 (M + H), 407.2 (M + Na), 439.2 (M + Na + MeOH). Calcd. for C 20 H 22 N 2 O 2 2 : C, 62.47 H, 5.24 N, 7.29. Found: C, 62.42 H, 5.29 N, 7.10. N-(5-Methyl-4-phenyl-3-tosylthiazolidin-2-ylidene)aniline (3n) Ts N NPh Yield: 38%. white solid. 1 H-NMR (300 MHz, CDCl 3 ): δ 1.19 (d, J = 6.6Hz, 3H), 2.46 (s, 3H), 5.01-5.10 (m, J = 6.6Hz, 1H), 5.14 (d, J = 6.6Hz, 1H), 6.82 (d, J = 7.8Hz, 2H), 7.07 (t, J = 7.5Hz, 1H), 7.26-7.35 (m, 9H), 8.05 (d, J = 8.1Hz, 2H). 13 C-NMR (75 MHz, CDCl 3 /TM): δ = 15.0, 21.6, 52.9, 61.5, 120.8, 124.2, 128.2, 128.5, 128.7, 128.8, 129.0, 129.1, 133.1, 136.2, 144.5, 149.9, 150.7. IR (KBr pellet): 1643, 1591, 1352, 1170, 1144, 1101 cm -1. M-EI (m /z): 423.2 (M + H), 445.2 (M + Na), 477.3 (M + Na + MeOH). Calcd. for C 23 H 22 N 2 O 2 2 : C, 65.35 H, 5.25 N, 6.63. Found: C, 65.31 H, 5.49 N, 6.72. -9

N-(3-Tosyl-4,5-cyclohexa[d]thiazolidin-2-ylidene)naphthalen-1-amine (3o) Ts N N Yield: 23%. 1 H-NMR (300 MHz, CDCl 3 ): δ 1.25-1.65 (m, 4H), 1.72-1.84 (m, 2H), 1.96 (d, J = 6.3Hz, 2H), 2.44 (s, 3H), 3.19-3.26 (m, 2H), 3.78 (td, J = 3Hz, 10.8Hz, 1H), 6.58 (d, J = 7.2Hz, 1H), 7.24-7.32 (m, 4H), 7.40-7.44 (m, 2H), 7.55 (d, J = 8.1Hz, 1H), 7.75 (d, J = 8.7Hz, 1H), 7.95 (d, J = 8.1Hz, 2H). 13 C-NMR (75 MHz, CDCl 3 ): δ = 21.6, 24.3, 25.1, 29.3, 32.4, 49.1, 70.4, 114.5, 123.7, 124.2, 125.2, 125.5, 126.1, 127.0, 127.5, 128.8, 129.2, 133.9, 136.0, 144.2, 146.5, 154.6. N-(3-Tosylhexahydrobenzo[d]thiazol-2(3H)-ylidene)butan-1-amine (3p) Ts N N Yield: 55%. Pale yellow solid. 1 H-NMR (300 MHz, CDCl 3 ): δ 0.823 (t, 7.2Hz, 3H), 1.09-1.17 (m, 2H), 1.33-1.73 (m, 7H), 1.84-1.96 (dd, J = 10.4Hz, 24.3Hz, 2H), 1.11 (d, J = 10.4Hz, 1H), 2.86-2.95 (td, J = 7.2Hz, 12.3Hz, 1H), 3.09-3.29 (m, 2H), 3.51 (td, J = 3.3Hz, 11.1Hz, 1H), 7.27 (d, J = 4.5Hz, 2H), 7.82 (d, J = 8.4Hz, 2H). 13 C-NMR (75 MHz, CDCl 3 ): δ = 13.8, 20.4, 21.5, 24.4, 25.2, 29.6, 32.4, 32.6, 48.8, 55.8, 69.7, 128.7, 128.8, 135.7, 143.9, 151.6. IR (KBr pellet): 2933, 2862, 1655, 1359, 1171, 1084 cm -1. M-EI (m /z): 367.1 (M + H). HRM (EI) Calcd. For C 18 H 27 N 2 O 2 2 +1 : 367.1508. Found: 367.1513. N-(5-(Chloromethyl)-1,3-oxathiolan-2-ylidene)aniline (6a) Cl O NPh In a chlenk tube equipped with condenser, n Bu 3 P (6.25 μl, 0.025 mmol) was added to a stirring, rt mixture of epoxide (0.25 mmol), phenyl isothiocyanate (60 μl, 0.5 mmol) and anhydrous acetonitrile (2 ml) under argon. Then heat the mixture to reflux for 24 hours. After then, the mixture was concentrated and the residue was purified by flash chromatography on silica gel using PE/EtOAc (10:1) as eluent to give 6a. Yield: 88%, pale yellow oil, 1 H-NMR (300 MHz, CDCl 3 ): δ 3.36-3.52 (m, 2H), 3.67-3.85 (m, 2H), 4.85 (td, J = 12 Hz, 12Hz, 1H), 6..96 (d, J = 7.2 Hz, 2H), 7.08-7.15 (m, 1H), 7.32 (t, J = 7.8 Hz, 2H). 13 C-NMR (75 MHz, CDCl 3 ): δ = 33.8, 42.7, 79.7, 124.0, 124.4, 129.1, 148.5, 162.4. IR -10

(film): 1755, 1597, 1500, 1481, 1301, 1180 cm -1. M-EI (m /z): 327.9 (M + H). HRM (EI) Calcd. For C 10 H 11 NOCl +1 : 228.0244. Found: 228.0252. 5-(Chloromethyl)-1,3-oxathiolane-2-thione (6b) Cl O In a eal tube equipped with condenser, n Bu 3 P (6.25 μl, 0.025 mmol) was added to a stirring, rt mixture of epoxide (0.25 mmol), carbon disulfide (60 μl, 1 mmol) and anhydrous acetonitrile (2 ml) under argon. Then heat the mixture to reflux for 24 hours. After then, the mixture was concentrated and the residue was purified by flash chromatography on silica gel using PE/EtOAc (10:1) as eluent to give 6b. Yield: 74%, yellow oil, 1 H-NMR (300 MHz, CDCl 3 ): δ 3.70-3.99 (m, 4H), 5.41 (td, J = 12.6 Hz, 10.2 Hz, 2H). 13 C-NMR (75 MHz, CDCl 3 ): δ = 36.6, 42.8, 79.7, 88.2. IR (film): 2953, 1736, 1437, 1340, 1184, 1041 cm -1. EI-M (m /z): 168. HRM (EI) Calcd. For C 4 H 5 ClO 2 : 167.9470. Found: 167.9471. References for supporting information: 1. Ando, T.; Kano, D.; Minakata,.; Ryu, N.; Komatsu, M. Tetrahedron, 1998, 54, 13485. 2. (a) Yamada, Y.; Yamamoto, T.; Okawara, M. Chem. Lett. 1975, 4, 361. (b) Evans, D. A.; Faul, M. M.; Bilodeau, M. T. J. Am. Chem. oc. 1994, 116, 2742. -11

Tributylphosphine-Catalyzed Cycloaddition of Aziridines with Carbon Disulfide and Isothiocyanate Jing-Yu Wu, Zhi-Bin Luo, Li-Xin Dai and Xue-Long Hou* tate Key Laboratory of Organometallic Chemistry, hanghai Institute of Organic Chemistry, Chinese Academy of ciences, 354 Fenglin Road, hanghai 200032, P. R. China E-mail: xlhou@mail.sioc.ac.cn 1 H & 13 C-NMR spectra -12