Copper-Catalyzed Alkene Aziridination with N-Tosyloxycarbamates

Transcription

1 Copper-Catalyzed Alkene Aziridination with -Tosyloxycarbamates élène Lebel,* Sylvain Lectard and Michaël Parmentier Département de chimie, Université de Montréal, Montréal, Québec, Canada, 3C 3J7 Supporting Information Table of Contents General information..s2 Preparation of Cu(pyridine) 4 (BF 4 ) 2...S2 General Procedures S3 Characterization of products S4 MR Spectra S11 S1

2 General: The commercially available alcohols were purified using standard methods prior to use. K 2 C 3 was purchased from Aldrich and finely powdered before use. Cu(BF 4 ) 2 was obtained from Cu(BF 4 ) 2 x 2 after drying under high vacuum for one week. Known copper complexes were prepared according to literature procedures. 1 Known allylic -hydroxycarbamates and allylic - tosyloxycarbamates were prepared according to literature procedure. 2 2,2,2-trichloroethyl-tosyloxycarbamate 10 was prepared according to a published procedure. 3 Analytical thin layer chromatography (TLC) was performed using EM Reagent 0.25 mm silica gel 60-F plates. Visualization of the developed chromatogram was performed by UV absorbance, aqueous cerium molybdate, ethanolic phosphomolybdic acid, or aqueous potassium permanganate. Flash chromatography was performed using EM Silica Gel 60 ( mesh) with the indicated solvent system. ptical rotations were measured on a Perkin-Elmer 341 digital polarimeter at 589 nm. Data are reported as follows: [α] D temp, concentration (c g/100ml), and solvent. Infrared spectra were recorded on a Perkin Elmer Spectrum ne FTIR spectrometer equipped with a Golden Gate Diamond ATR and are reported in reciprocal centimeters (cm-1). nly the most important and relevant frequencies are reported. 1 MR spectra were recorded in CDCl 3, unless otherwise noted, on a Bruker AV-400, a Bruker ARX-400, a Bruker AMX-300 or a Bruker AV-300 spectrometers (400, 400, 300 and 300 Mz respectively). Chemical shifts are reported in ppm on the δ scale from an internal standard of residual chloroform (7.26 ppm). Data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, qn = quintet, m = multiplet and br = broad), coupling constant in z, integration. 13 C MR spectra were recorded in CDCl 3, unless otherwise noted, on a Bruker AV-400, a Bruker ARX-400, a Bruker AMX-300 or a Bruker AV-300 spectrometers (100, 100, 75 and 75 Mz respectively) with complete proton decoupling. Chemical shifts are reported in ppm from the central peak of CDCl 3 (76.9 ppm) on the δ scale. Mass spectra were obtained on a LC-MSD TF (ESI) Agilent Technologies high resolution from the Centre régional de spectrométrie de masse de l Université de Montréal. 2+ Cu(BF 4 ) 2 Cu 2BF 4 - Tetrakis(pyridine) copper (II) bis(tetrafluoroborate) To a suspension of copper tetrafluoroborate (II) (1.19 g, 5.00 mmol) in benzene (50 ml) was added distilled pyridine (8.10 ml, 100 mmol). The heterogeneous solution was heated to 80 C for 15 min then cooled to room temperature. The purple suspension was stirred for 24 hours. Ether (50 ml) was added and the blue solid was then filtered, washed with ether and dried under reduced pressure, affording the desired complex (2.67 g, 97%) as a light purple solid. Monocrystals were obtained by diffusing dichloromethane into acetonitrile and were resolved by X-ray crystal structure analysis 1 (a) aynes, J. S.; Rettig, S. J.; Sams, J. R.; Trotter, J.; Thompson, R. C. Inorg. Chem. 1988, 27, (b) Mohr, F.; Binfield, S. A.; Fettinger, J. C.; Vedernikov, A.. J. rg. Chem. 2005, 70, Lebel,.; uard, K.; Lectard, S. J. Am. Chem. Soc. 2005, 127, Lebel,.; uard, K. rg. Lett. 2007, 9, S2

3 Procedure A: Preparation of allylic -hydroxycarbamates 4 The unsaturated alcohol (25.0 mmol) was dissolved at room temperature in DCM (50 ml). Carbonyl diimidazole (4.46 g, 27.5 mmol) was added in one portion and the solution was stirred for 1 h. The solution was washed with a saturated solution of 4 Cl (3x50 ml). The organic layer was dried over MgS 4, filtered and concentrated to give an oil. The previous oil was dissolved in pyridine (85 ml) at room temperature and 2 Cl (5.21 g, 75.0 mmol) was added in one portion. The solution was stirred for 3 h. DCM (100 ml) was added followed by a 10% solution of sulphuric acid (125 ml). The two layers were separated and the organic layer was washed with 10% solution of sulphuric acid (3 x 150 ml), then dried over MgS 4, filtered and concentrated. The product was purified by flash chromatography on silica gel using AcEt/hexanes as eluent or recrystallized from chloroform/hexanes. Procedure B: Preparation of allylic -hydroxycarbamates 5 The unsaturated alcohol (25.0 mmol) was dissolved at room temperature in C 3 C (150 ml). Carbonyl diimidazole (4.86 g, 30.0 mmol) was added in one portion and the solution was stirred for 90 min. 2 Cl (8.67 g, 125 mmol) was added in one portion followed by imidazole (6.81 g, 100 mmol). The solution was stirred for 3 h and a 10% solution of sulphuric acid was added until p~2-3. A biphasic colorless solution was obtained. The organic layer was removed and the aqueous layer was extracted with ether (4x100 ml) and the organic layers were dried over MgS 4, filtered and concentrated. The product was purified by flash chromatography on silica gel using AcEt/hexanes as eluent or recrystallized from chloroform/hexanes. Procedure C: Preparation of allylic -tosyloxycarbamates The -hydroxycarbamate (25.0 mmol) was dissolved in Et 2 (50 ml). p-toluenesulfonyl chloride (4.76 g, 25.0 mmol) was added in one portion at 0 C. The solution was stirred for 15 min then a solution of Et 3 (3.20 ml, 22.5 mmol) in Et 2 (5 ml) was slowly added at such a rate that the solution remained acidic at all time. A white precipitate rapidly appeared. The solution was filtrated and the remaining solid washed with ether. The combined filtrate was concentrated under reduced pressure. The product was purified by flash chromatography on silica gel using AcEt/hexanes as eluent or recrystallized from chloroform/hexanes. Procedure D: Catalytic intramolecular aziridination The -tosyloxycarbamate ( mmol), K 2 C 3 (692 mg, 5.00 mmol), and Cu(pyridine) 4 (Tf) 2 (14 mg, mmol,) were dissolved in acetone (20 ml) at 25 C. The mixture was vigorously stirred for 16 h after which time DCM was added. The solution was filtered over celite to remove the potassium tosylate salt. The filtrate was concentrated and the residue was subjected to flash chromatography on silica gel using AcEt/hexanes as eluent. Procedure E: Catalytic intermolecular aziridination Cu(pyridine) 4 (BF 4 ) 2 (28 mg, mmol) was suspended in benzene (5 ml) in a 20 ml scintillation vial under air. K 2 C 3 (692 mg, 5.00 mmol) and the olefin (2.50 mmol) were successively added. The heterogeneous solution was stirred for 15 min at 25 C and 10 (182 mg, 0.50 mmol) was added in one portion. The solution was stirred at 25 C overnight. Ether (15 ml) was added and the resulting mixture was filtered. The solid was washed 4 times with 10 ml of ether. The combined filtrate was concentrated under reduced pressure. The residue is purified by flash chromatography on silica gel using Ether/hexanes as eluent. The silica gel was pre-treated with 1% Et 3 /hexanes. 4 Sparks, S. M.; Vargas, J. D.; Shea, K. J. rg. Lett. 2000, 2, Donohoe, T. J.; Chughtai, M. J.; Klauber, D. J.; Griffin, D.; Campbell, A. D. J. Am. Chem. Soc. 2006, 128, S3

4 Characterization of allylic -hydroxycarbamates Ph Ph S4 (E)-3-Phenylprop-2-ene -hydroxycarbamate The title compound was prepared from (E)-cinnamyl alcohol (6.71 g, 50.0 mmol) according to the general procedure A. The desired -hydroxycarbamate (6.86 g, 71%) was obtained as a white solid after recrystallization. R f 0.22 (40% AcEt/hexanes); mp C. 1 MR (400 Mz, CDCl 3 ) δ 7.42 (s, 1), (m, 5), 7.28 (s (br), 1), 6.65 (d, J = 16 z, 1), 6.26 (dt, J = 16, 7 z, 1) 4.80 (dd, J = 7, 1 z, 2); 13 C MR (100 Mz, CDCl 3 ) δ 159.1, 135.8, 134.7, 128.5, 128.1, 126.6, 122.4, 66.7; IR (neat) 3317, 3251, 2897, 1698, 1510, 1450, 1304, 1273, 1121, 972, cm -1 ; MRS (ESI) calc. for C a [M+a] + : ; found: Methyl-6,6-dimethyl-bicyclo[3.1.1]hept-2-ene -hydroxycarbamate The title compound was prepared from (-)-myrtenol (3.81 g, 25.0 mmol) according to the general procedure A. The desired -hydroxycarbamate (5.20 g, 98%) was obtained as a white solid after flash chromatography (30% AcEt/hexanes - 55% AcEt/hexanes). R f 0.24 (35% AcEt/hexanes); mp C; [α] D 25 = (c 1.59, DCM); 1 MR (400 Mz, CDCl 3 ) δ 7.46 (s (br), 1), 7.34 (s (br), 1), 5.58 (s, 1), (m, 2), (m, 1), (m, 2), (m, 2), 1.27 (s, 3), 1.15 (d, J = 9 z, 1), 0.80 (s, 3); 13 C MR (100 Mz, CDCl 3 ) δ 159.3, 142.2, 121.9, 68.4, 43.0, 40.2, 37.7, 31.1, 30.9, 25.7, 20.7; IR (neat) 3284 (br), 2985, 2913, 2831, 1714, 1468, 1265, 1111, 770 cm -1 ; MRS (ESI) calc. for C a [M+a] + : ; found: n-pr (Z)-ex-2-ene -hydroxycarbamate The title compound was prepared from (E)-hex-2-en-1-ol (2.00 g, 20.0 mmol) according to the general procedure B. The desired -hydroxycarbamate (2.79 g, 88%) was obtained as a pale yellow oil after flash chromatography (30% AcEt/hexanes-55% AcEt/hexanes). R f 0.29 (40% AcEt/hexanes); 1 MR (400 Mz, CDCl 3 ) δ 7.52 (s (br), 2), 5.64 (dt, J = 11, 7 z, 1), 5.52 (dt, J = 11, 7 z, 1), 4.68 (d, J = 7 z, 2), 2.06 (q, J = 7 z, 2), 1.38 (sextuplet, J = 7 z, 2), 0.89 (t, J = 7 z, 3); 13 C MR (100 Mz, CDCl 3 ) δ 159.4, 135.7, 122.8, 61.9, 29.3, 22.4, 13.5; IR (neat) 3294 (br), 2959, 2931, 2872, 1711, 1463, 1261, 1112, 1034 cm -1 ; MRS (ESI) calc. for C a [M+a] + : ; found: Characterization of -tosyloxycarbamates n-pr Ph Ph Ts (E)-3-Phenylprop-2-ene - tosyloxycarbamate The title compound was prepared from (E)-3-phenylprop-2-ene -hydroxycarbamate (3.00 g, 15.5 mmol) according to the general procedure C. The desired -tosyloxycarbamate (4.86 g, 90%) was obtained as a white solid after flash chromatography (10% AcEt/hexanes-50% AcEt/hexane). R f

5 0.53 (35% AcEt/hexanes); mp C; 1 MR (400 Mz, CDCl 3 ) δ 7.87 (d, J = 8 z, 2), 7.75 (s (br), 1), (m, 7), 6.55 (d, J = 16 z, 1), 6.07 (dt, J = 16, 7 z, 1), 4.66 (dd, J = 7, 1 z, 2), 2.36 (s, 3); 13 C MR (100 Mz, CDCl 3 ) δ 155.1, 146.0, 135.6, 135.1, 130.0, 129.6, 129.4, 128.5, 128.3, 126.5, 121.4, 67.3, 21.6; IR (neat) 3173, 2948, 1762, 1732, 1595, 1489, 1364, 1252, 1197, 1181, 963, 733, 689 cm -1 ; MRS (ESI) calc. for C S [M+a] + : ; found: Ts 2-Methyl-6,6-dimethyl-bicyclo[3.1.1]hept-2-ene -tosyloxycarbamate The title compound was prepared from 2-methyl-6,6-dimethyl-bicyclo[3.1.1]hept-2-ene -hydroxycarbamate ( g, 4.7 mmol) according to the general procedure C. The desired -tosyloxycarbamate (1.27 g, 73%) was obtained as an oil after flash chromatography (10% AcEt/hexanes- 50% AcEt/hexanes). R f 0.26 (DCM); [a] D 25 = (c 0.98, DCM); 1 MR (300 Mz, CDCl 3 ) δ (m, 3), 7.36 (d, J = 8 z, 2), 5.47 (s (br), 1), (m, 2), 2.46 (s, 3), (m, 3), (m, 1), 1.99 (dt, J = 6, 1 z, 1), 1.26 (s, 3), 1.10 (d, J = 9 z, 1), 0.75 (s, 3); 13 C MR (75 Mz, CDCl 3 ) δ 155.3, 145.9, 141.7, 130.2, 129.6, 129.4, 122.7, 69.4, 43.1, 40.4, 37.9, 31.3, 31.1, 25.9, 21.7, 20.8; IR (neat) 3276 (br), 2919, 1744, 1597, 1456, 1386, 1232, 1192, 1179, 1091, 813, 738, 661 cm -1 ; MRS (ESI) calc. for C Sa [M+a] + : ; found: n-pr (Z)-ex-2-ene -tosyloxycarbamate (8) The title compound was prepared from (Z)-hex-2-ene -hydroxycarbamate (2.79 g, 17.5 mmol) according to the general procedure C. The desired -tosyloxycarbamate (3.53 g, 64%) was obtained as a colorless oil after flash chromatography (10% AcEt/hexanes-50% AcEt/hexanes). R f 0.54 (35% AcEt/hexanes); 1 MR (400 Mz, CDCl 3 ) δ 8.33 (s, 1), 7.84 (d, J = 8 z, 2), 7.33 (d, J = 8 z, 2), (m, 1), (m, 1), 4.52 (d, J = 7 z, 2), 2.43 (s, 3), 1.98 (q, J = 8 z, 2), 1.34 (sextuplet, J = 7 z, 2), 0.85 (t, J = 7 z, 3); 13 C MR (100 Mz, CDCl 3 ) δ 155.5, 145.9, 135.9, 130.0, 129.5, 129.3, 122.0, 62.5, 29.2, 22.2, 21.5, 13.4; IR (neat) 3275 (br), 2959, 2931, 2872, 1740, 1740, 1597, 1460, 1379, 1192, 1179, 1090, 815, 743, 662, 630 cm -1 ; MRS (ESI) calc. for C Sa [M+a] + : ; found: Characterization of aziridines Ph Ts 6-Phenethyl-3-oxa-1-aza-bicyclo[3.1.0]hexan-2-one (1) The title compound was prepared from (E)-3-phenylprop-2-ene -tosyloxycarbamate (375 mg, mmol) according to the general procedure D. The desired aziridine (171 mg, 84%) was obtained as a light yellow oil after flash chromatography (30% AcEt/hexanes). R f 0.44 (40% AcEt/hexanes); 1 MR (400 Mz, CDCl 3 ) δ (m, 2), (m, 3), (m, 2), (m, 1), (m, 2), (m, 2), (m, 1); 13 C (100 Mz, CDCl 3 ) δ 166.9, 140.2, n-pr 8 Ph Ts 1 S5

6 128.5, 128.3, 126.2, 66.5, 46.5, 43.7, 32.8, 32.4; IR (neat) 2920, 1781, 1455, 1372, 1231, 1144, 1102, 1054, 980, 814, 703 cm -1 ; MRS (ESI) calc. for C a [M+a] + : ; found: n-pr Ts trans-6-propyl-3-oxa-1-aza-bicyclo[3.1.0]hexan-2-one (2) 6 The title compound was prepared from (E)-hex-2-ene -tosyloxycarbamate (313 mg, mmol) according to the general procedure D. The desired aziridine (93 mg, 66%) was obtained as a light yellow oil after flash chromatography (30% AcEt/hexanes-50% AcEt/hexanes). R f 0.18 (35% AcEt/hexanes); 1 MR (400 Mz, CDCl 3 ) δ 4.43 (dd, J = 9, 2 z, 1), 4.39 (dd, J = 9, 5 z, 1), (m, 1), (m, 1), (m, 4), 0.95 (t, J = 7 z, 3); 13 C (100 Mz, CDCl 3 ) δ 167.1, 66.5, 48.2, 43.5, 32.9, 19.5, 13.5; IR (neat) 2960, 2919, 2875, 2850, 1782, 1463, 1375, 1233, 1142, 1095, 1034, 976, 811 cm -1 ; MRS (ESI) calc. for C a [M+a] + : ; found: Ph Ts 6-Phenyl-3-oxa-1-aza-bicyclo[3.1.0]hexan-2-one (3) The title compound was prepared from (E)-3-phenylprop-2-ene - tosyloxycarbamate (347 mg, mmol) according to the general procedure D. The desired aziridine (89 mg, 51%) was obtained as a white solid after flash chromatography (30% AcEt/hexanes). R f 0.43 (40% AcEt/hexanes); mp C; 1 MR (400 Mz, CDCl 3 ) δ (m, 3), (m, 2), 4.61 (dd, J = 10, 1 z 1), 4.51 (dd, J = 10, 5 z, 1), 3.36 (d, J = 3 z, 1), (m, 1); 13 C (100 Mz, CDCl 3 ) δ 166.5, 134.2, (2C), 126.2, 67.1, 48.1, 46.1; IR (neat) 2983, 2916, 1752, 1371, 1146, 1083, 1047, 978, 813, 754, 701, 666 cm -1 ; MRS (ESI) calc. for C [M+] + : ; found: Ts 6-Methyl-6-(4-methylpentyl-3-enyl)-3-oxa-1-aza-bicyclo[3.1.0]hexan2-one (4) 7 Sodium tetra[3,5-di(trifluoromethyl)phenyl]borate (88 mg, 0.10 mmol) and CuCl 2 (Pyridine) 2 (14 mg, mmol) were dissolved in DCM (20 ml) and stirred at 25 C for 4 h. The green solution was concentrated to dryness, affording a green solid. Acetone (20 ml) was added followed by K 2 C 3 (692 mg, 5.00 mmol) and (E)-3,7-dimethyl-octa-2,6-diene -tosyloxycarbamate (367 mg, mmol). The mixture was vigorously stirred for 16 h after which time DCM was added. The solution was filtered over celite and the filtrate was concentrated. The desired aziridine (116 mg, 61%) was obtained as light yellow oil after flash chromatography (30% AcEt/hexanes). R f 0.24 (35% AcEt/hexanes); 1 MR (400 Mz, CDCl 3 ) δ (m, 1), 4.50 (dd, J = 10, 6 z, 1), 4.26 (dd, J = 10, 2 z, 1), 3.04 (dd, J = 6, 2 z, 1), (m, 2), (m, 2), 1.67 (s, 3), 1.60 (s, 3), 1.37 (s, 3); 13 C (100 Mz, CDCl 3 ) δ 165.5, 132.6, 122.6, 64.5, 50.9, 48.8, 38.5, 25.5, 23.6, 17.6, 12.0; IR (neat) 2971, 2916, 1777, 1454, 1160, 1231, 1093, 1076, 820, cm -1. n-pr Ph 3 2 Me 4 6 Bergmeier, S. C.; Stanchina, D. M. J. rg. Chem. 1997, 62, Kolohang, A.; Stanchina, C. L.; Coates, R. M. Tetrahedron 1999, 55, S6

7 Ts Tetrahydro-2-oxa-3a-azacyclopenta[1,3]cyclopropa[1,2]benzen-3-one (5) 8 The title compound was prepared from cyclohexene-1-methane -tosyloxycarbamate (327 mg, mmol) according to the general procedure D. The desired aziridine (123 mg, 79%) was obtained as a light yellow oil after flash chromatography (30% AcEt/hexanes). R f 0.21 (35% AcEt/hexanes); 1 MR (400 Mz, CDCl 3 ) δ 4.42 (d, J = 9 z, 1), 4.06 (dd, J = 9, 1 z, 1), 2.70 (dd, J = 4, 1 z, 1), (m, 2), (m, 2), (m, 1), (m, 3); 13 C (100 Mz, CDCl 3 ) δ 167.9, 70.2, 48.8, 48.5, 24.7, 24.1, 20.3, 19.1; IR (neat) 2937, 2865, 1770, 1438, 1219, 1131, 1036, 939, 631 cm -1. Ts 3-xa-1-azaspiro[bicyclo[3.1.0]hexane-6,1'-cyclohexan]-2-one (6) The title compound was prepared from 2-cyclohexylidene -tosyloxycarbamate (339 mg, mmol) according to the general procedure D. The desired aziridine (140 mg, 84%) was obtained as a light yellow oil after flash chromatography (30% AcEt/hexanes-50% AcEt/hexanes). R f 0.20 (40% AcEt/hexane); 1 MR (400 Mz, CDCl 3 ) δ 4.47 (dd, J = 10, 6 z, 1), 4.25 (dd, J = 10, 2 z, 1), 3.00 (dd, J = 6, 2 z, 1), (m, 4), (m, 6); 13 C MR (100 Mz, CDCl 3 ) δ 165.4, 64.2, 53.6, 49.3, 35.3, 25.1, 25.0, 24.2, 24.1; IR (neat) 2934, 2859, 1760, 1449, 1372, 1160, 1146, 1087, 1050, 1001, 819 cm -1 ; MRS (ESI) calc. for C a [M+a] + : ; found: Ts 7 (1R,2R,7S,9R)-10,10-Dimethyl-4-oxa-6-azatetracyclo[ ,6.02,7]undecan-5-one (7) The title compound was prepared from 2-methyl-6,6-dimethyl-bicyclo[3.1.1]hept-2-ene - tosyloxycarbamate (365 mg, mmol) according to the general procedure D using 5 mol% of Cu(pyridine) 4 (Tf) 2. The desired aziridine (151 mg, 78%) was obtained as white solid after flash chromatography (30% AcEt/hexanes). R f 0.32 (DCM); mp C; [α] D 25 = -8.3 (c, DCM); 1 MR (300 Mz, CDCl 3 ) δ 4.46 (d, J = 9 z, 1), 4.15 (d, J = 9 z, 1), 2.75 (d, J = 5 z, 1), (m, 2), (m, 2), (m, 1), 1.77 (d, J = 10 z, 1), 1.31 (s, 3), 0.98 (s, 3); 13 C MR (75 Mz, CDCl 3 ) δ 166.5, 70.3, 53.1, 45.7, 41.6, 40.5, 40.1, 27.0, 26.5, 25.6, 20.4; IR (neat) 2993, 2972, 2941, 1784, 1140, 1043 cm -1 ; MRS (ESI) calc. for C [M+] + : ; found: Padwa, A.; Flick, A. C.; Leverett, C. A.; Stengel, T. J. rg. Chem. 2004, 69, S7

8 n-pr 8 Ts 2,2,2-Trichloroethyl 2-(4-fluorophenyl)aziridine-1-carboxylate (13) The title compound was prepared from 10 (182 mg, mmol) and 1-fluoro-4-vinylbenzene (300 µl, 2.50 mmol) according to the general procedure E. The desired aziridine (86 mg, 55%) was obtained as colorless oil after flash chromatography (2% ether/hexanes-10% ether/hexanes). R f 0.32 (15% EtAc/hexanes); 1 MR (400 Mz, CDCl 3 ) δ (m, 2), (m, 2), 4.83 (d, J S8 n-pr + 9 n-pr 2 1 : 2.8 cis-6-propyl-3-oxa-1-aza-bicyclo[3.1.0]hexan-2-one (9) 6 The title compound was prepared from (Z)-hex-2-ene -tosyloxycarbamate (313 mg, mmol) according to the general procedure D. The desired aziridine was obtained as a mixture of diastereomers (cis:trans 1:2.8) and as a light yellow oil (77 mg, 55%) after flash chromatography (30% AcEt/hexanes-50% AcEt/hexanes). After further purification, a pure sample of the cis aziridine was obtained. R f 0.16 (35% AcEt/hexanes); 1 MR (400 Mz, CDCl 3 ) δ 4.54 (dd, J = 10, 6 z, 1), 4.27 (dd, J = 10, 2 z, 1), (m, 1), 2.73 (dd, J = 9, 3 z, 1), (m, 4), (t, J = 7 z, 3); 13 C MR (100 Mz, CDCl 3 ) δ 165.3, 64.1, 45.7, 42.6, 25.3, 20.1, 13.7; IR (neat) 2962, 2874, 1769, 1372, 1262, 1167, 1137, 1088, 1031 cm -1 ; MRS (ESI) calc. for C a [M+a] + : ; found: Ts + Cl 3 C 10 2,2,2-Trichloroethyl 2-phenylaziridine-1-carboxylate (11) The title compound was prepared from 10 (182 mg, mmol) and styrene (290 µl, 2.50 mmol) according to the general procedure E. The desired aziridine (108 mg, 74%) was obtained as a white solid after flash chromatography (1% ether/hexanes-10% ether/hexanes). R f 0.42 (15% EtAc/hexanes); mp C; 1 MR (300 Mz, CDCl 3 ) δ (m, 5), 4.84 (d, J = 12 z, 1), 4.74 (d, J = 12 z, 1), 3.64 (dd, J = 6, 4 z, 1), 2.82 (d, J = 6 z, 1), 2.44 (d, J = 4 z, 1); 13 C MR (75 Mz, CDCl 3 ) δ 161.3, 136.1, 128.5, 128.0, 126.1, 94.8, 75.3, 39.7, 35.1; IR (neat) 3004, 1735, 1170, 907, 731 cm -1 ; MRS (ESI) calc. for C Cl 3 2 [M+] + : ; found Ts + Cl 3 C 10 2,2,2-Trichloroethyl 2-p-tolylaziridine-1-carboxylate (12) The title compound was prepared from 10 (182 mg, mmol) and 1-methyl-4-vinylbenzene (330 µl, 2.50 mmol) according to the general procedure E. The desired aziridine (112 mg, 68%) was obtained as a colorless oil after flash chromatography (hexanes-5% ether/hexanes). R f 0.53 (15% EtAc/hexanes); mp C; 1 MR (400 Mz, C 6 D 6 ) δ 7.07 (d, J = 8 z, 2), 6.91 (d, J = 8 z, 2); 4.53 (d, J = 12 z, 1), 4.42 (d, J = 12 z, 1), 3.27 (dd, J = 6, 4 z, 1), 2.32 (d, J = 6 z, 1), 2.06 (s, 3), 1.95 (d, J = 4 z, 1); 13 C MR (100 Mz, C 6 D 6 ) δ 161.4, 137.8, 134.0, 129.5, 126.6, 95.7, 75.4, 40.0, 35.2, 21.1; IR (neat) 3001, 2954, 1733, 1391, 1296, 1277, 1165, 817, 718 cm -1 ; MRS (ESI) calc. for C Cl 3 2 [M+] + : ; found Ts + Cl 3 C 10 F F 11 Troc Troc Troc

9 = 12 z, 1), 4.75 (d, J = 12 z, 1), 3.61 (dd, J = 6, 4 z, 1), 2.81 (d, J = 6 z, 1), 2.39 (d, J = 4 z, 1); 13 C MR (100 Mz, CDCl 3 ) δ (d, J = 250 z), 161.2, (d, J = 3 z); (d, J = 8 z), (d, J = 22 z), 94.7, 75.3, 39.1, 35.1; 19 F MR (282 Mz, CDCl 3 ) δ (tt, J = 9, 5 z, 1F); IR (neat) 3003, 2956, 1733, 1513, 1389, 1156, 818, 715 cm -1 ; MRS (ESI) calc. for C Cl 3 F 2 [M+] + : ; found Ts + Cl 3 C 10 Cl 2,2,2-Trichloroethyl 2-(4-chlorophenyl)aziridine-1-carboxylate (14) The title compound was prepared from 10 (182 mg, mmol) and 1-chloro-4-vinylbenzene (300 µl, 2.50 mmol) according to the general procedure E. The desired aziridine (101 mg, 62%) was obtained as colorless oil after flash chromatography (2% ether/hexanes-10% ether/hexanes). R f 0.27 (15% EtAc/hexanes); 1 MR (400 Mz, CDCl 3 ) δ 7.34 (d, J = 8 z, 2), 7.28 (d, J = 8 z, 2), 4.85 (d, J = 12 z, 1), 4.77 (d, J = 12 z, 1), 3.62 (dd, J = 6, 3.5 z, 1), 2.84 (d, J = 6 z, 1), 2.40 (d, J = 3.5 z, 1); 13 C MR (100 Mz, CDCl 3 ) δ 161.1, 134.7, 133.8, 128.6, 127.5, 94.7, 75.3, 39.0, 35.2; IR (neat) 3000, 2955, 1738, 1495, 1388, 1308, 1290, 1168, 1091, 824, 720 cm -1 ; MRS (ESI) calc. for C Cl 4 2 [M+] + : ; found Ts + Cl 3 C 10 Br 2,2,2-Trichloroethyl 2-(4-bromophenyl)aziridine-1-carboxylate (15) The title compound was prepared from 10 (182 mg, mmol) and 1-bromo-4-vinylbenzene (320 µl, 2.50 mmol) according to the general procedure E. The desired aziridine (105 mg, 56%) was obtained as colorless oil after flash chromatography (2% ether/hexanes-10% ether/hexanes). R f 0.29 (15% EtAc/hexanes); 1 MR (400 Mz, CDCl 3 ) δ 7.48 (d, J = 8 z, 2), 7.20 (d, J = 8 z, 2), 4.82 (d, J = 12 z, 1), 4.75 (d, J = 12 z, 1), 3.58 (dd, J = 6, 4 z, 1), 2.82 (d, J = 6 z, 1), 2.38 (d, J = 4 z, 1); 13 C MR (100 Mz, CDCl 3 ) δ 161.1, 135.3, 131.6, 127.8, 122.0, 94.7, 75.3, 39.1, 35.2; IR (neat) 3000, 2954, 1737, 1385, 1307, 1290, 1167, 1070, 1011, 821, 719 cm -1 ; MRS (ESI) calc. for C BrCl 3 2 [M+] + : ; found Ts + Cl 3 C 10 Me Me 2,2,2-Trichloroethyl 2-(3-methoxyphenyl)aziridine-1-carboxylate (16) The title compound was prepared from 10 (182 mg, mmol) and 3-methoxy-4-vinylbenzene (350 µl, 2.50 mmol) according to the general procedure E. The desired aziridine (95 mg, 62%) was obtained as colorless oil after flash chromatography (2% ether/hexanes-15% ether/hexanes). R f 0.21 (15% EtAc/hexanes); 1 MR (400 Mz, C 6 D 6 ) δ 6.98 (t, J = 8 z, 1), (m, 1), (m, 1), 6.65 (ddd, J = 8, 3, 1 z, 1), 4.48 (d, J = 12 z, 1), 4.40 (d, J = 12 z, 1), 3.23 (s, 3), (m,1), 2.27 (dd, J = 6, 0.5 z, 1), 1.89 (dd, J = 4, 0.5 z, 1); 13 C MR (100 Mz, C 6 D 6 ) δ 161.3, 160.5, 138.5, 129.9, 118.9, 114.1, 111.9, 95.7, 75.4, 54.8, 40.0, 35.3; IR (neat) 3002, 2955, 2837, 1738, 1604, 1400, 1302, 1204, 1181 cm -1 ; MRS (ESI) calc. for C Cl 3 2 [M+] + : ; found Cl Br Troc Troc Troc S9

10 Ts + Cl 3 C ,2,2-Trichloroethyl 2-(4-nitrophenyl)aziridine-1-carboxylate (17) The title compound was prepared according to the general procedure E. The desired aziridine (86 mg, 51%) was obtained as a yellow oil after flash chromatography (15% AcEt/hexanes). R f 0.13 (15% EtAc/hexanes); 1 MR (400 Mz, CDCl 3 ) δ 8.15 (d, J = 9 z, 2), 7.51 (d, J = 9 z, 2), 4.84 (d, J = 12 z, 1), 4.78 (d, J = 12 z, 1), 3.71 (dd, J = 6, 3 z, 1), 2.91 (d, J = 6 z, 1), 2.41 (d, J = 3 z, 1); 13 C MR (100 Mz, C 6 D 6 ) δ 160.8, 147.6, 143.7, 127.0, 123.8, 94.6, 75.4, 38.6, 35.8; IR (neat) 2956, 1738, 1605, 1520, 1346, 1169 cm -1 ; MRS (MAB) calcd for C Cl [M+] + : ; found Troc CCl Phenylaziridine (18). 9 To a solution of 2,2,2-trichloroethyl 2-phenylaziridine-1-carboxylate (146 mg, mmol) in mixture of acetonitrile (5 ml) methanol (2 ml) was added Li 2 (105 mg, 2.50 mmol) and water (0.090 ml, 5.0 mmol). After 5 hours of stirring at 23 C, 2 (5 ml) and AcEt (15 ml) were added and the two layers were separated. The aqueous layer was washed with AcEt (3 x 15 ml). The combined organic layers were washed with brine (20 ml), dried over MgS 4 and concentrated to give the desired aziridine 18 (44 mg, 74%) as a colorless oil after flash chromatography (AcEt). R f 0.35 (100% AcEt). 1 MR (400 Mz, C 6 D 6 ) δ (m, 5), 2.46 (m, 1), 1.58 (m, 1), 1.34 (m, 1), 0.15 (br, 1); 13 C MR (100 Mz, CDCl 3 ) δ 140.3, 128.4, 127.0, 125.6, 32.1, CCl 3 2-(4-nitrophenyl)aziridine (19). To a solution of 2,2,2-trichloroethyl 2-(4-nitrophenyl)aziridine-1-carboxylate (167 mg, mmol) in mixture of acetonitrile (5 ml) methanol (2 ml) was added Li. 2 (105 mg, 2.50 mmol) and water (0.090 ml, 5.0 mmol). After 5 hours of stirring at 23 C, 2 (5 ml) and AcEt (15 ml) were added and the two layers were separated. The aqueous layer was washed with AcEt (3 x 15 ml). The combined organic layers were washed with brine (20 ml), dried over MgS 4 and concentrated to give the desired aziridine 19 (74 mg, 91%) as yellow oil after flash chromatography (100% AcEt). R f 0.33 (AcEt). 1 MR (400 Mz, CDCl 3 ) δ 8.16 (d, J = 9 z, 2), 7.40 (d, J = 9 z, 2), 3.14 (d, J = 3 z, 1), 2.37 (d, J = 6 z, 1), 1.73 (s, 1), 1.14 (br, 1); 13 C MR (100 Mz, CDCl 3 ) δ 148.5, 147.0, 126.4, 123.6, 31.2, IR (neat) 3312, 3064, 2992, 1601, 1515, 1344, 1109, 851 cm -1 ; MRS (MAB) calcd for C [M+] + : ; found Alonso, D. A.; Andersson, P. G. J. rg. Chem. 1998, 63, S10

11 ppm, (CDCl3, 400 Mz) S11

12 ppm, (CDCl3, 100 Mz) S12

13 ppm, (CDCl3, 400 Mz) S13

14 ppm, (CDCl3, 100 Mz) S14

15 ppm, (CDCl3, 400 Mz) S15

16 ppm, (CDCl3, 100 Mz) S16

17 ppm, (CDCl3, 400 Mz) S S

18 ppm, (CDCl3, 100 Mz) S18 S

19 ppm, (C6D6, 100 Mz) S S

20 ppm, (CDCl3, 75 Mz) S20 S

21 ppm, (CDCl3, 400 Mz) S S21

22 ppm, (CDCl3, 100 Mz) S22 S

23 ppm, (CDCl3, 300 Mz) Ph 1 S23

24 S24 Ph ppm, (CDCl3, 75 Mz)

25 ppm, (CDCl3, 400 Mz) ppm, (CDCl3, 400 Mz) n-pr 2 S25

26 S n-pr ppm, (CDCl3, 100 Mz)

27 ppm, (CDCl3, 400 Mz) Ph 3 S27

28 S Ph ppm, (CDCl3, 100 Mz)

29 ppm, (CDCl3, 400 Mz) Me 4 S29

30 S30 Me ppm, (CDCl3, 100 Mz)

31 S ppm, (CDCl3, 400 Mz)

32 S ppm, (CDCl3, 100 Mz)

33 S ppm, (CDCl3, 400 Mz)

34 S ppm, (CDCl3, 100 Mz)

35 S ppm, (CDCl3, 300 Mz)

36 S ppm, (CDCl3, 75 Mz)

37 ppm, (CDCl3, 400 Mz) n-pr 9 S37

38 S38 n-pr ppm, (CDCl3, 100 Mz)

39 S39 Troc ppm, (CDCl3, 300 Mz)

40 S40 0 Troc ppm, (CDCl3, 75 Mz)

41 S41 Troc ppm, (C6D6, 400 Mz)

42 S42 Troc ppm, (C6D6, 100 Mz)

43 S43 Troc F ppm, (CDCl3, 400 Mz)

44 S44 Troc F ppm, (CDCl3, 100 Mz)

45 S45 Troc F ppm, (CDCl3, 282 Mz)

46 S46 Troc Cl ppm, (CDCl3, 400 Mz)

47 S47 Troc Cl ppm, (CDCl3, 100 Mz)

48 S48 Troc Br ppm, (CDCl3, 400 Mz)

49 S49 Br 15 Troc ppm, (CDCl3, 100 Mz)

50 ppm, (C6D6, 400 Mz) Troc Me 16 S50

51 S51 0 Troc Me ppm, (C6D6, 100 Mz)

52 ppm (t1) S52 2 CCl

53 ppm (t1) S53 2 CCl 3 17

54 ppm (t1) ppm (t1) S

55 150 ppm (t1) S55 18

56 ppm (t1) ppm (t1) S

57 ppm (t1) S