ࡱ> xzw7 AsbjbjUU "7|7|9>$l:R,   8N $R  "4 4 4 G G G 1333333$D! d#WUG C G G G W~~4 4 G N~84 4 1G 1.4  `?4 0#S#~~~~Supporting information Enamide-Olefin Ring-Closing Metathesis Sape S. Kinderman,a Jan H. van Maarseveen,a Hans E. Schoemaker,a,b Henk Hiemstraa and Floris P. J. T. Rutjes* a,c General Unless otherwise noted, materials were purchased from commercial suppliers and used without purification. Toluene, ethylene dichloride, dichloromethane and acetonitrile were freshly distilled from calcium hydride. Tetrahydrofuran was freshly distilled from sodium with benzophenone as indicator. Triethylamine was stored over potassium hydroxide pellets and used as such. Column chromatography was performed using Fluka Chemika silica gel (0.04-0.063 mm, enriched with ~ 0.1 % Ca). Infrared spectra were recorded on a Bruker IFS 28 spectrophotometer. Nuclear magnetic resonance (NMR) spectra were obtained on a Bruker ARX 400 or a Varian Inova-500. Spectra are reported in units of ppm on the ( scale, relative to chloroform (7.26 ppm for 1H-NMR and 77.0 ppm for 13C-NMR). Mass spectra were measured using a JEOL JMS SX/SX102A four-sector mass spectrometer, coupled to a JEOL MS-MP7000 data system. 1-amino-3-butene, 1-amino-4-pentene and 1-amino-5-hexene were prepared according to literature procedures. The aldimines 5 and 7 were prepared analogous to the procedure of Campbell et al. The ketimines 6, 8 and 9 were prepared by refluxing the corresponding amine (1 eq.) with the carbonyl compound (1.1 eq.) in pentane during 24-48 hours with a waterseparator. The solvent was then removed and the crude imine was used immediately. Phenyl propadienyl ether 21 was prepared following the procedure described by Brandsma et al. The amides 33 and 34 were synthesized via standard (K2CO3, MeCN, reflux) alkylation of 4-methyl-N-pent-4-enyl-benzenesulfonamide with propargyl bromide and 1-bromo-2-butyne respectively. Synthesis of the precursors 10-20 All precursors were prepared analogous to the following representative procedure. To a solution of the freshly prepared imine 8 (0.5 g, 4.0 mmol) in toluene (5 mL) at 0 C under a nitrogen atmosphere was added Et3N (0.56 mL, 4 mmol), followed by adding Ts2O (1.31 g, 4 mmol). The reaction was stirred at this temperature for 1 hour. The cloudy mixture was allowed to warm to room temperature and stirred for another 2 hours. Formation of product could be observed by TLC (pentane/diethyl ether 4:1, anisaldehyde staining, Rf = 0.32). The solvent was evaporated and the oily residue was purified with flash column chromatography (pentane/diethyl ether 10:1 - 8:1 + 0.1% Et3N) to give N-isopropenyl-4-methyl-N-pent-4-enylbenzenesulfonamide 15 (0.584 g, 52% yield). IR (CH2Cl2) n 3066 cm 1, 2930, 2360, 1643, 1342, 1161; 1H NMR (C6D6, 500 MHz) d 1.44-1.50 (m, 2 H), 1.74 (s, 3H), 1.88 (s, 3H), 1.93-1.97 (m, 2H), 3.25 (t, J = 7.1 Hz, 2H), 4.61 (s, 1H), 4.70 (s, 1H), 4.95 (d, J = 10.0 Hz, 1H), 4.99 (d, J = 17 Hz, 1H), 5.66-5.71 (m, 1H), 6.76 (d, J = 8.0 Hz, 2H), 7.73 (d, J = 8.0 Hz, 2H); 13C NMR (C6D6, 125 MHz) d 21.45, 22.82, 28.16, 31.28, 48.89, 114.0, 115.70, 129.70, 137.49, 138.23, 143.06, 143.66; HRMS (FAB+) calcd. for C15H22NO2S (M + H): 280.1371, found 280.1368. N-But-3-enyl-4-methyl-N-vinylbenzenesulfonamide 10 (14% yield). Rf = 0.34 (pentane/Et2O, 4:1); IR (CH2Cl2) n 3066 cm 1, 1625, 1356, 1166; 1H NMR (C6D6, 500 MHz) d 1.85 (s, 3H), 2.22-2.26 (m, 2H), 3.24 (t, J = 7.7 Hz, 2H), 4.00 (d, J = 15.9 Hz, 1H), 4.12 (d, J = 9.3 Hz, 1H), 4.88 (s, 1H), 4.92 (s, 1H), 5.53-5.60 (m, 1H), 6.73 (d, J = 8.3 Hz, 2H), 7.06 (dd, J = 9.3, 15.9 Hz, 1H), 7.60 (d, J = 8.1 Hz, 2H); 13C NMR (C6D6, 125 MHz) d 21.41, 31.90, 44.70, 92.62, 117.29, 127.51, 130.16, 133.01, 135.07, 137.76, 143.70; HRMS (FAB+) calcd. for C13H18NO2S (M + H): 252.1058, found 252.1067. N-But-3-enyl-N-isopropenyl-4-methylbenzenesulfonamide 11 (37% yield). Rf = 0.35 (petroleum ether 60-80/methyl t-butyl ether 4:1); IR (CH2Cl2) n 3066 cm 1, 2927, 2361, 1645, 1342, 1161, 1092; 1H NMR (C6D6, 400 MHz) d 1.76 (s, 3H), 1.88 (s, 3H), 2.10-2.16 (m, 2H), 3.30 (t, J = 7.3 Hz, 2H), 4.55 (s, 1H), 4.69 (s, 1H), 4.96 (d, J = 3.8 Hz, 1H), 4.99 (d, J = 10.7 Hz, 1H), 5.59-5.68 (m, 1H), 6.75 (d, J = 8.0 Hz, 2H), 7.71 (d, J = 8.3 Hz, 2H); 13C NMR (C6D6, 125 MHz) d 21.45, 22.96, 33.40, 49.04, 114.02, 117.27, 128.43, 129.70, 135.54, 137.39, 143.10, 143.76; HRMS (FAB+) calcd. for C14H20NO2S (M + H): 266.1215, found 266.1224. N-But-3-enyl-N-isopropenylbenzamide 12 (40% yield). Rf = 0.26 (pentane/Et2O 2:1); IR (CH2Cl2) n 3688 cm 1, 3082, 2981, 2360, 1633, 1397; 1H NMR (C6D6, 500 MHz) d 1.44 (s, 3H), 2.33-2.37 (m, 2H), 3.62 (t, J = 7.5 Hz, 2H), 4.39 (s, 1H), 4.40 (s, 1H), 5.00 (d, J = 10.3 Hz, 1H), 5.05 (d, J = 17.3 Hz, 1H), 5.75-5.82 (m, 1H), 7.04-7.07 (m, 3H), 7.54-7.56 (m, 2H); 13C NMR (C6D6, 125 MHz) d 21.70, 33.09, 46.68, 114.04, 116.94, 128.49, 128.69, 130.12, 136.31, 138.38, 145.35, 170.28; HRMS (FAB+) calcd. for C14H18NO (M + H): 216.1388, found 216.1395. N-But-3-enyl-N-isopropenyl ethyl carbamate 13 (30% yield). Rf = 0.43 (pentane/Et2O 2:1); IR (CH2Cl2) n 2982 cm 1, 2360, 1695, 1652; 1H NMR (C6D6, 500 MHz) d 0.99 (t, J = 7.1 Hz, 3H), 1.84 (s, 3H), 2.23-2.28 (m, 2H), 3.47 (t, J = 7.3 Hz, 2H), 4.05 (q, J = 7.1 Hz, 2H), 4.66 (s, 1H), 4.69 (s, 1H), 4.96 (d, J = 10.3 Hz, 1H), 5.01 (d, J = 15.4 Hz, 1H), 5.67-5.73 (m, 1H); 13C NMR (C6D6, 125 MHz) d 15.00, 22.03, 33.83, 48.91, 61.58, 110.25, 116.87, 136.18, 145.60, 155.31; HRMS (FAB+) calcd. for C10H18NO2 (M + H): 184.1338, found 184.1343. 4-Methyl-N-pent-4-enyl-N-vinylbenzenesulfonamide 14 (5% yield). Rf = 0.36 (pentane/Et2O 4:1); IR (CH2Cl2) n 3056 cm 1, 2927, 2362, 1354, 1267, 1165; 1H NMR (C6D6, 500 MHz) d 1.64-1.68 (m, 2H), 1.92-1.98 (m, 2H), 1.99 (s, 3H), 3.26 (t, J = 7.4 Hz, 2H), 4.12 (d, J = 15.6 Hz, 1H), 4.23 (d, J = 9.3 Hz, 1H), 4.97-5.02 (m, 2H), 5.67-5.72 (m, 1H), 6.89 (d, J = 8.3 Hz, 2H), 7.13 (dd, J = 9.3, 15.9 Hz, 1H), 7.70 (d, J = 8.3 Hz, 2H); 13C NMR (C6D6, 125 MHz) d 21.49, 26.56, 31.40, 44.76, 92.81, 115.79, 127.50, 130.24, 133.12, 137.60, 138.03, 143.85; HRMS (FAB+) calcd. for C14H20NSO2 (M + H): 266.1215, found 266.1224. N-Isopropenyl-N-pent-4-enylbenzamide 16 (44% yield). Rf = 0.47 (pentane/Et2O 1:1); IR (CH2Cl2) n 3063 cm 1, 2937, 1632, 1398; 1H NMR (C6D6, 400 MHz) d 1.46 (s, 3H), 1.65-1.72 (m, 2H), 1.97-2.02 (m, 2H), 3.56 (t, J = 7.6 Hz, 2H), 4.38 (s, 1H), 4.40 (s, 1H), 4.98 (d, J = 10.2 Hz, 1H), 5.04 (d, J = 17.1 Hz, 1H), 5.72-5.80 (m, 1H), 7.03-7.06 (m, 3H), 7.53-7.56 (m, 2H); 13C NMR (C6D6, 125 MHz) d 21.64, 27.75, 31.80, 46.75, 113.82, 115.41, 128.68, 130.07, 138.47, 138.62, 145.38, 170.16; HRMS (FAB+) calcd. for C15H20NO (M + H): 230.1545, found 230.1540. N-Pent-4-enyl-N-isopropenyl ethyl carbamate 17 (41% yield). Rf = 0.26 (pentane/Et2O 2:1); IR (CH2Cl2) n 2982 cm 1, 2934, 1693, 1652; 1H NMR (C6D6, 500 MHz) d 1.00 (t, J = 7.1 Hz, 3H), 1.58-1.62 (m, 2H), 1.84 (s, 3H), 1.91-1.94 (m, 2H), 3.40 (t, J = 7.6 Hz, 2H), 4.06 (q, J = 7.1 Hz, 2H), 4.67 (s, 1H), 4.70 (s, 1H), 4.95 (d, J = 10.3 Hz, 1H), 5.00 (d, J = 17.1 Hz, 1H), 5.69-5.74 (m, 1H); 13C NMR (C6D6, 125 MHz) d 15.03, 22.00, 28.56, 31.58, 49.00, 61.54, 110.14, 115.33, 138.56, 145.61, 155.11. N-Hex-5-enyl-N-isopropenyl-4-methylbenzenesulfonamide 18 (48% yield). Rf = 0.31 (pentane/Et2O 4:1); IR (CH2Cl2) n 3067 cm 1, 2934, 2865, 2361, 1644, 1342, 1161, 1092; 1H NMR (C6D6, 500 MHz) d 1.25-1.32 (m, 2H), 1.36-1.42 (m, 2H), 1.76 (s, 3H), 1.89 (s, 3H), 1.90-1.93 (m, 2H), 3.25 (t, J = 7.0 Hz, 2H), 4.63 (s, 1H), 4.72 (s, 1H), 4.95-5.02 (m, 2H), 5.66-5.72 (m, 1H), 6.78 (d, J = 8.3 Hz, 2H), 7.74 (d, J = 8.3 Hz, 2H); 13C NMR (C6D6, 125 MHz) d 21.45, 22.82, 26.39, 28.27, 33.87, 49.22, 113.91, 115.26, 128.68, 129.70, 137.60, 138.99, 143.05, 143.67; HRMS (FAB+) calcd. for C16H24NO2S (M + H): 294.1528, found 294.1533. N-Hex-5-enyl-N-isopropenylbenzamide 19 (63% yield). Rf = 0.28 (pentane/Et2O 1:1); IR (CH2Cl2) n 3051 cm 1, 2936, 2861, 2360, 1632, 1399; 1H NMR (C6D6, 500 MHz) d 1.31-1.36 (m, 2H), 1.49 (s, 3H), 1.56-1.63 (m, 2H), 1.98 (q, J = 7.2 Hz, 2H), 3.55 (t, J = 7.6 Hz, 2H), 4.40 (s, 1H), 4.42 (s, 1H), 4.98 (d, J = 10.0 Hz, 1H), 5.03 (d, J = 17.1 Hz, 1H), 5.72-5.77 (m, 1H), 7.05 (br s, 3H), 7.55 (br s, 2H); 13C NMR (C6D6, 125 MHz) d 21.67, 26.89, 28.03, 34.17, 47.04, 113.72, 115.19, 128.48, 128.68, 130.04, 138.53, 139.18, 145.44, 170.14; HRMS (FAB+) calcd. for C16H22NO (M + H): 244.1701, found 244.1701. N-Hex-5-enyl-N-isopropenyl ethyl carbamate 20 (68% yield). Rf = 0.29 (pentane/Et2O, 4:1); IR (CH2Cl2) n 2981 cm 1, 2935, 1693, 1652; 1H NMR (C6D6, 500 MHz) d 1.00 (t, J = 7.1 Hz, 3H), 1.22-1.28 (m, 2H), 1.47-1.53 (m, 2H), 1.85 (s, 3H), 1.90-1.94 (m, 2H), 3.39 (t, J = 7.5 Hz, 2H), 4.06 (q, J = 7.1 Hz, 2H), 4.68 (s, 1H), 4.71 (s, 1H), 4.93-5.00 (m, 2H), 5.69-5.73 (m, 1H); 13C NMR (C6D6, 125 MHz) d 15.05, 22.04, 26.65, 28.77, 34.09, 49.26, 61.52, 110.05, 115.14, 139.13, 145.67, 155.11; HRMS (FAB+) calcd. for C12H22NO2 (M + H): 212.1651, found 212.1643. N-But-3-enyl-4-methyl-N-(3-phenoxypropenyl)benzenesulfonamide 24 To a solution of amide 22 (1.0 g, 4.44 mmol) in dry acetonitrile (15 mL) under a nitrogen atmosphere was added Et3N (0.93 mL, 6.7 mmol, 1.5 equiv.), phenyl propadienyl ether (0.65 g, 4.9 mmol, 1.1 equiv.), dppp (91 mg, 5 mol%) and Pd(OAc)2 (50 mg, 5 mol%). The mixture was stirred at room temperature for 24 h. TLC (pentane/petroleum ether 60-80 1:1, anisaldehyde staining, Rf = 0.52) indicated complete conversion. H2O (25 mL) and diethyl ether (25 mL) was added, followed by layer separation. The aqueous layer was extracted with diethyl ether (3 x 20 mL) and the combined organic layers were washed with brine (25 mL), dried over Na2SO4 and concentrated. Flash column chromatography (pentane/diethyl ether 8:1 - 4:1 + 0.1% Et3N) afforded 24 as a colorless oil (0.644 g, 41%). IR (CH2Cl2) n 3079 cm 1, 2927, 1658, 1598, 1495, 1358, 1167; 1H NMR (C6D6, 500 MHz) d 1.79 (s, 3H), 2.15-2.20 (m, 2H), 3.15 (t, J = 7.7 Hz, 2H), 4.08 (d, J = 6.1 Hz, 2H), 4.70-4.75 (m, 1H), 4.83-4.87 (m, 2H), 5.47-5.53 (m, 1H), 6.65 (d, J = 8.3 Hz, 2H), 6.79-6.82 (m, 3H), 7.07-7.10 (m, 3H), 7.55 (d, J = 8.3 Hz, 2H); 13C NMR (C6D6, 125 MHz) d 21.45, 31.82, 45.40, 67.45, 104.80, 115.59, 117.43, 121.33, 127.50, 130.09, 130.27, 131.36, 134.91, 137.48, 143.95, 159.46; HRMS (FAB+) calcd. for C20H24NO3S (M + H): 358.1477, found 358.1473. Ring closing metathesis, synthesis of cyclic enamides 25-32 A typical procedure for the ring closing metathesis is as follows. Precursor 10 (80 mg, 0318 mmol) was dissolved in freshly distilled and degassed CH2Cl2 (20 mL) under argon atmosphere. This solution was again degassed using argon and then the ruthenium catalyst (13 mg, 0.016 mmol) was added. After 24 hours of reflux the conversion was complete as indicated by TLC (pentane/Et2O 4:1, anisaldehyde staining, Rf = 0.14). The solvent was removed in vacuo and flash column chromatography (pentane/Et2O 4:1 + 0.1% Et3N) of the crude oil gave the cyclic enamide 1-(toluene-4-sulfonyl)-2,3-dihydro-1H-pyrrole 25 (60.0 mg, 84% yield). IR (CH2Cl2) n 2927 cm 1, 2864, 1614, 1598, 1350, 1167; 1H NMR (C6D6, 500 MHz) d 1.81 (t, J = 9.2 Hz, 2H), 1.88 (s, 3H), 3.21 (t, J = 9.2 Hz, 2H), 4.59 (d, J = 4.1 Hz, 1H), 6.36 (s, 1H), 6.80 (d, J = 8.1 Hz, 2H), 7.66 (d, J = 8.3 Hz, 2H); 13C NMR (C6D6, 125 MHz) d 21.46, 29.89, 47.71, 111.08, 128.47, 130.02, 131.65, 134.45, 143.72; HRMS (FAB+) calcd. for C11H14NO2S (M + H): 224.0745, found 224.0743. 5-Methyl-1-(toluene-4-sulfonyl)-2,3-dihydro-1H-pyrrole,8 26 (86% yield). Rf = 0.32 (pentane/Et2O 4:1); IR (CH2Cl2) n 2929 cm 1, 1317, 1264, 1165; 1H NMR (C6D6, 500 MHz) d 1.65-1.69 (m, 2H), 1.85 (s, 3H), 2.06 (s, 3H), 3.59 (t, J = 8.8 Hz, 2H), 6.74 (d, J = 8.3 Hz, 2H), 7.69 (d, J = 8.0 Hz, 2H); 13C NMR (C6D6, 125 MHz) d 15.96, 21.45, 27.45, 50.89, 111.21, 128.11, 130.03, 136.64, 140.64, 143.41; HRMS (FAB+) calcd. for C12H16NO2S (M + H): 238.0902, found 238.0903. (5-Methyl-2,3-dihydropyrrol-1-yl)phenylmethanone 27 (63% yield). Rf = 0.33 (pentane/ethyl acetate 2:1); IR (CH2Cl2) n 3049 cm 1, 2929, 2863, 1667, 1626, 1407; 1H NMR (C6D6, 500 MHz) d 1.93 (br m, 2H), 2.02 (br s, 3H), 3.48 (br s, 2H), 4.64 (s, 1H), 7.02-7.08 (m, 3H), 7.36-7.38 (m, 2H); 13C NMR (C6D6, 125 MHz) d 16.84, 27.83, 51.42, 110.91, 128.14, 128.49, 128.56, 130.16, 138.89, 168.53; HRMS (FAB+) calcd. for C12H14NO (M + H): 188.1075, found 188.1070. 5-Methyl-2,3-dihydropyrrole-1-carboxylic acid ethyl ester 28 (62% yield). Rf = 0.36 (pentane/Et2O 2:1); 1H NMR (C6D6, 500 MHz) d 1.00 (t, J = 7.1 Hz, 3H), 2.00-2.05 (m, 2H), 2.17 (br s, 3H), 3.59 (br s, 2H), 4.03 (q, J = 7.1 Hz, 2H), 4.45 (s, 1H); 13C NMR (C6D6, 125 MHz) d 15.10, 16.26, 27.20, 48.33, 61.05, 128.68, 136.58, 153.50. 1-(Toluene-4-sulfonyl)-1,2,3,4-tetrahydropyridine8 29 (80% yield). Rf = 0.24 (pentane/Et2O 4:1); IR (CH2Cl2) n 2931 cm 1, 2851, 1649, 1339, 1264, 1167, 1102; 1H NMR (C6D6, 500 MHz) d 1.17-1.20 (m,2H), 1.39-1.43 (m, 2H), 1.90 (s, 3H), 3.17 (t, J = 5.5 Hz, 2H), 4.65-4.68 (m, 1H), 6.80 (d, J = 8.1 Hz, 2H), 6.81 (d, J = 8.1 Hz, 1H), 7.66 (d, J = 8.3 Hz, 2H); 13C NMR (C6D6, 125 MHz) d 21.35, 21.38, 21.48, 44.35, 108.25, 126.12, 127.79, 130.12, 136.61, 143, 57; HRMS (FAB+) calcd. for C12H16NO2S (M + H): 238.0902, found 238.0910. 6-Methyl-1-(toluene-4-sulfonyl)-1,2,3,4-tetrahydropyridine 30 (75% yield). Rf = 0.37 (pentane/Et2O 4:1); IR (CH2Cl2) n 3063 cm 1, 2934, 2361, 1344, 1162; 1H NMR (C6D6, 500 MHz) d 1.06 (m, 2H), 1.47 (m, 2H), 1.88 (s, 3H), 2.22 (s, 3H), 3.48 (t, J = 5.4 Hz, 2H), 4.68 (br s, 1H), 6.78 (d, J = 8.3 Hz, 2H), 7.69 (d, J = 8.3 Hz, 2H); 13C NMR (C6D6, 125 MHz) d 21.08, 21.46, 23.12, 23.90, 47.42, 113.59, 127.74, 130.04, 135.13, 139.22, 143.23; HRMS (FAB+) calcd. for C13H18NO2S (M + H): 252.1058, found 252.1051. (6-Methyl-3,4-dihydro-2H-pyridin-1-yl)phenylmethanone8 31 (93% yield). Rf = 0.26 (pentane/Et2O 2:1); IR (CH2Cl2) n 2932 cm 1, 1631, 1390, 1268; 1H NMR (C6D6, 500 MHz) d 1.28-1.32 (m, 2H), 1.71-1.74 (m, 2H), 1.97 (br s, 3H), 3.35 (t, J = 5.4 Hz, 2H), 4.74 (br s, 1H), 7.02-7.07 (m, 3H), 7.53-7.55 (m, 2H); 13C NMR (C6D6, 125 MHz) d 22.52, 23.52, 24.07, 47.21, 112.97, 128.74, 128.99, 130.59, 137.26, 138.42, 170.09; HRMS (FAB+) calcd. for C13H16NO (M + H): 202.1232, found 202.1250. 6-Methyl-3,4-dihydro-2H-pyridine-1-carboxylic acid ethyl ester 32 (57% yield). Rf = 0.32 (pentane/Et2O 8:1); IR (CH2Cl2) n 2983 cm 1, 2933, 1694, 1660, 1404, 1382, 1339, 1268, 1254, 1194; 1H NMR (C6D6, 500 MHz) d 0.98 (t, J = 7.1 Hz, 3H), 1.40-1.42 (m, 2H), 1.70-1.72 (m, 2H), 2.19 (s, 3H), 3.51 (t, J = 5.4 Hz, 2H), 4.04 (q, J = 7.1 Hz, 2H), 4.67 (s, 1H); 13C NMR (C6D6, 125 MHz) d 14.93, 23.18, 23.58, 23.64, 45.25, 61.65, 111.27, 136.58, 154.71; HRMS (FAB+) calcd. for C9H16NO2 (M + H): 170.1181, found 170.1198. Synthesis of the allenamides. The following procedure is representative for the formation of the allenamides. Amide 34 (0.5 g, 1.8 mmol) was dissolved in dry THF (5 mL) under a nitrogen atmosphere. t-BuOK (40 mg, 0.36 mmol) was added resulting in a dark solution, which was stirred for 64 h. Formation of product could be observed by TLC (pentane/diethyl ether 4:1, anisaldehyde staining, Rf = 0.38). The solvent was evaporated and the residue was dissolved in diethyl ether, followed by filtration over basic alumina. The solvent was again evaporated and the crude oil was purified by flash column chromatography (pentane/diethyl ether 10:1 - 8:1 + 0.1% Et3N) to give 4-methyl-N-pent-4-enyl-N-propa-1,2-dienylbenzenesulfonamide 35 (0.43 g, 86% yield). IR (CH2Cl2) n 3066 cm 1, 2923, 2257, 1360, 1170; 1H NMR (C6D6, 500 MHz) d 1.54-1.67 (m, 2 H), 2.04-2.09 (m, 2H), 2.43 (s, 3H), 3.11 (t, J = 7.3 Hz, 2H), 4.96 (d, J = 10.3 Hz, 1H), 5.02 (d, J = 17.1 Hz, 1H), 5.29 (d, J = 6.1 Hz, 2H), 5.75-5.8 (m, 1H), 6.83 (t, J = 6.2 Hz, 1H), 7.31 (d, J = 8.1 Hz, 2H), 7.68 (d, J = 8.3 Hz, 2H); 13C NMR (C6D6, 125 MHz) d 21.55, 27.05, 30.64, 46.10, 87.49, 100.17, 115.10, 127.15, 129.70, 135.51, 137.65, 143.60, 201.47; HRMS (FAB+) calcd. for C15H20NO2S (M + H): 278.1215, found 278.1209. () Sato, T.; Nakamura, N.; Ikeda, K.; Okada, M.; Ishibashi, H.; Ikeda, M. J. Chem. Soc. Perkin Trans. I 1992, 2399. () Gagn, M. R.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1992, 114, 275. () Tamaru, Y.; Hojo, M.; Higashimura, H.; Yoshida, Z. J. Am. Chem. Soc. 1988, 110, 3994. () Campbell, K. N.; Sommers, A. H.; Campbell, B. K. J. Am. Chem. Soc. 1944, 66, 82. () L. Brandsma, H. D. Verkruijsse, Synthesis of acetylenes, allenes and cumulenes, a laboratory manual in Studies in Organic Chemistry vol. 8, Elsevier, Amsterdam, 1981, p. 94. () hman, J.; Somfai, P. Tetrahedron 1992, 48, 9537. () Hegedus, L. S.; McKearin, J. M. J. Am. Chem. Soc. 1982, 104, 2444. () Kim, S.; Yoon, J. Synthesis 2000, 1622. () IR and mass data could not be obtained due to the instability of the compound. PAGE  PAGE 7 ?STklstQRef{|          T U a c h j  3   2 3 > ? 6CJH*OJQJ5CJOJQJ6CJOJQJ]CJH*OJQJ5CJOJQJ\j0JCJOJQJUCJH*OJQJ jdCJOJQJ CJOJQJH*\CJ \@(@A 3 VXvw  H$J$)$da$dd]d] dxx] Hdxx]H$Hdxx]Ha$p%s>s@s .Z\hjnptv68  XZ"$(*.0@Dln~6CJH*OJQJ]CJH*OJQJ CJOJQJ6CJOJQJ5CJOJQJ\56CJOJQJ\] CJOJQJCJH*OJQJH&(\^$&df:;IKLNPQvwxbdtvxzpr46VZj6CJOJQJ6CJH*OJQJ56CJOJQJ]5CJOJQJCJH*OJQJ6CJOJQJ] CJOJQJ CJOJQJCJH*OJQJFjlnpTVrvx|8:`b~fh    . 0 n 5CJOJQJ6CJOJQJ]6CJH*OJQJ]5CJOJQJ\56CJOJQJ\]CJH*OJQJ CJOJQJ CJOJQJCJH*OJQJD !!.!0!2!4!J!L!`!b!!! 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