Supporting Information for C(sp)-C(sp 3 ) Bond Formation through Cu-Catalyzed Cross-Coupling of N-Tosylhydrazones and Trialkylsilylethyne Fei Ye, Xiaoshen Ma, Qing Xiao, Huan Li, Yan Zhang, Jianbo Wang*,, Beijing National Laboratory of Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China Email: wangjb@pku.edu.cn CONTENTS 1) General... S2 2) General procedure for the preparation of N-tosylhydrazones. S2 3) Optimization of the Reaction Conditions.... S2 4) General procedure for the Cu(I)-catalyzed cross-coupling... S3 5) Procedure for the use of syringe pump and one-pot synthesis S3 6) Spectra data for products....... S4 7) References.......... S14 8) 1 H NMR and 13 C NMR spectra for the products. S15 S1
1) General All reactions were performed under a nitrogen atmosphere in a 25 ml Schlenk tube. Dioxane was dried over Na before use. For chromatography, 200-300 mesh silica gel (Qingdao, China) was employed. 1 H NMR and 13 C NMR spectra were recorded on Varian 300 or Brucker ARX 400 spectrometer in CDCl 3 solution and the chemical shifts were reported in parts per million (δ) relative to internal standard (0 ppm). IR spectra were recorded on Nicolet is10. EI-MS were recorded on Agilent 7890A/5975C. N-Tosylhydrazones was prepared by literature procedure. 1 Unless otherwise noted, materials obtained from commercial suppliers were used without further purification. 2) General procedure for the preparation of N-tosylhydrazones N-Tosylhydrazones was prepared according to literature procedure. 1 Typical procedure. A solution of pure TsNHNH 2 (5 mmol) in methanol (5 ml) was stirred and heated to 60 o C until the TsNHNH 2 was completely dissolved. Then carbonyl compounds were dropped to the mixture slowly. After approximately 5-30 min the crude products was obtained as precipitates. The precipitates were washed by petroleum ether then were dried in vacuo to afford the pure products. The reaction provides the N-tosylhydrazones 1a-o, 5a-t in about 85-99% yields. 3) Optimization of the Reaction Conditions a H [Cu] Ph NNHTs Ph 1a 2a 3a Ph 4 H not observed entry ratio cat. (mol%) base (equiv) solvent yield b (1a:2a) (%) 1 c 1:1 CuBr 2 (10) LiO t Bu (2) dioxane 12 2 c 1:1 CuBr 2 (10) KO t Bu (2) toluene trace 3 1:1 CuBr 2 (10) Cs 2 CO 3 (2) dioxane trace 4 c 1.2:1 CuI (10) LiO t Bu (2.25) dioxane 17 5 c 1.2:1 CuI (10) LiO t Bu (2.5) dioxane 20 6 d 1.8:1 CuI (20) LiO t Bu (3) dioxane 51 7 d 2.2:1 CuI (10) LiO t Bu (3.5) dioxane 25 8 d 2.2:1 CuI (15) LiO t Bu (3.5) dioxane 40 9 d 2.2:1 CuI (20) LiO t Bu (3.5) dioxane 75 11 e 2.2:1 CuI (20) LiO t Bu (3.5) dioxane 42 a Without otherwise noted, the reaction were carried out under following conditions: 1a (0.2 mmol), solvent (2 ml), heating at 90 o Cfor1h;:trimethylsilyl. b Isolated yield. c The temperature of thereactionwas110 o C. d 1a (0.4 mmol), solvent (5 ml). e Solvent (10 ml). With N-tosylhydrazone 1a and trimethylsilylethyne 2a as the substrates, it was found that the S2
alkyne product 3a could be isolated in 12% yield with CuBr 2 as the catalyst in the presence of and LiO t Bu (entry 1). Changing the base to KO t Bu or Cs 2 CO 3 resulted in the formation of 3a only in trace amount (Table 1, entries 2, 3). Further optimization studies identified that the reaction gave slightly improved yield with CuI as catalyst (entry 4). Furthermore, it was found that substrate ratio, the CuI loading, and the amount of LiO t Bu all affected the reaction. With the increased ratio of 1a to 2a, catalyst loading, and the amount of LiO t Bu, the reaction could proceed with better yields (entries 5-9). The concentration of the reaction was also found to significantly affect the reaction. Under diluted concentration, the yield was diminished (entry 11). Under the optimized reaction conditions, the ethynylation product 3a could be isolated in 75 % yield (entry 9). 4) General procedure for the Cu(I)-catalyzed cross-coupling CuI (15.28 mg, 20 mol%), LiO t Bu (1.4 mmol, 112 mg) and N-tosylhydrazone 1 (0.88 mmol) were suspended in dioxane (5 ml) in a 25 ml Schlenk tube under nitrogen. Then terminal alkyne 2a or 2b (0.4 mmol) were added. The resulting solution was stirred at 90 o C for 1 h. After cooling to room temperature, the resulting mixture was filtered through a short path of silica gel, eluting with hexane and CH 2 Cl 2. The volatile compounds were removed in vacuo and the residue was purified by column chromatography (SiO 2, hexane). 5) Procedure for the use of syringe pump and one-pot synthesis In the case of 6x, 6y, 6z, we first prepared the solution of CuI (15.28 mg, 20 mol%), LiO t Bu (1.4 mmol, 112 mg) in dioxane (1 ml) in a 25 ml Schlenk tube under nitrogen, then terminal alkyne 2a or 2b (0.4 mmol) were added. Then the solution of N-tosylhydrazone 5x, 5y, 5z (0.88 mmol) in dioxane (4 ml) were added to sealed Schlenk tube via syringe pump for 1 h, the solution was stirred at 110 o C. After cooling to room temperature, the resulting mixture was filtered through a short path of silica gel, eluting with hexane and CH 2 Cl 2. The volatile compounds were removed in vacuo and the residue was purified by column chromatography (SiO 2, hexane). Aldehydes (2.2 mmol) or ketones (2.2 mmol) and 4-methylbenzenesylfonhydrazide (2.2 mmol, 409.2 mg) were suspended in dioxane (5 ml) in a 100 ml Schlenk tube, the resulting solution was stirred at 60 o C for 0.5 h. Upon completion, a solution of CuI (152.8 mg, 20 mol%), LiO t Bu (22 mmol, 1.76 g) in dioxane (35 ml) was added under nitrogen. Then terminal alkyne 2a or 2b (4 mmol) were added. The resulting solution was stirred at 110 o C for 1 h. After cooling to room temperature, the mixture was filtered through a short path of silica gel, eluting with hexane and CH 2 Cl 2. The volatile compounds were removed in vacuo and the crude residue was purified by column chromatography (SiO 2, hexane). Note: Excess amount of LiO t Bu was used in order to remove the H 2 O generated in the formation of N-tosylhydrazones from ketones or aldehydes. S3
6) Spectra data for the products Trimethyl(3-phenylprop-1-ynyl)silane (3a) 2 1 H NMR (400 MHz, CDCl 3 ) δ 0.11 (s, 9H), 3.58 (s, 2H), 7.13-7.22 (m, 2H), 7.24-7.28 (m, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.87, 26.9, 87.7, 105.1, 127.3, 128.6, 129.2, 137.2. 4-(3-(Trimethylsilyl)prop-2-ynyl)benzonitrile (3b) 3 Trimethyl(3-(3-nitrophenyl)prop-1-ynyl)silane (3c) 1 H NMR (400 MHz, CDCl 3 ) δ 0.12 (s, 9H), 3.63 (s, 2H), 7.39 (d, J = 8.4 Hz, 2H), 7.54 (d, J = 8.4 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 26.7, 88.8, 102.5, 111.0, 119.1, 129.0, 132.6, 142.3. 1 H NMR (400 MHz, CDCl 3 ) δ 0.14 (s, 9H), 3.68 (s, 2H), 7.42 (t, J = 8.0 Hz, 1H), 7.61 (d, J = 7.6 Hz, 1H), 8.03 (d, J = 8.0 Hz, 1H), 8.17 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 26.2, 89.1, 102.5, 122.1, 123.3, 129.7, 134.3, 138.9, 148.8; IR (film) 2957, 2179, 1532, 1349, 1251, 843 cm -1 ; EI-MS (m/z, relative intensity): 233 (M +, 8), 218 (100), 173 (17), 128 (7), 73 (6); HRMS (ESI) calcd. for C 12 H 16 NO 2 Si [(M+H) + ] 234.0945, found: 234.0949. N,N-Dimethyl-4-(3-(trimethylsilyl)prop-2-ynyl)benzenamine (3d) N 1 H NMR (400 MHz, CDCl 3 ) δ 0.10 (s, 9H), 2.85 (s, 6H), 3.48 (s, 2H), 6.64 (d, J = 8.4 Hz, 2H), 7.13 (d, J = 8.4 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.87, 25.0, 40.7, 85.9, 105.3, 112.8, 124.2, 128.3, 149.3; IR (film) 2940, 2160, 1544, 1325, 843, 760 cm -1 ; EI-MS (m/z, relative intensity): 231 (M +, 100), 216 (33), 198 (29), 158 (51), 134 (18), 108 (22), 73 (46); HRMS (ESI) calcd. for C 14 H 22 NSi [(M+H) + ] 232.1516, found: 232.1514. Trimethyl(3-(4-(4,4,6,6-tetramethyl-1,3,2-dioxaborinan-2-yl)phenyl)prop-1-ynyl)silane (3e) 1 H NMR (400 MHz, CDCl 3 ) δ 0.02 (s, 9H), 1.2 (s, 12H), 3.50 (s, 2H), 7.19 (d, J = 8.0 Hz, 2H), 7.61 (d, J = 8.0 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.05, 22.7, 24.9, 83.7, 87.0, 104.1, 125.3, 127.3, 135.1, 139.7; IR (film) 2917, 2849, 2179, 1361, 844 cm -1 ; EI-MS (m/z, relative intensity): 314 (100), 288 (60), 215 (53), 199 (91), 172 (56), 83 (55); HRMS (EI) calcd. for C 18 H 27 BO 2 Si [M + ] 314.1873, found: 314.1879. S4
(3-(Biphenyl-2-yl)prop-1-ynyl)trimethylsilane (3f) 1 H NMR (400 MHz, CDCl 3 ) δ 0.07 (s, 9H), 3.45 (s, 2H), 7.13-7.15 (m, 1H), 7.19-7.33 (m, 7H), 7.54 (d, J = 7.2 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 24.9, 86.9, 105.2, 126.9, 127.3, 127.9, 128.4, 129.1, 129.4, 130.1, 134.2, 141.2, 141.7; IR (film) 2958, 2177, 1495, 1250, 1022, 842, 760 cm -1 ; EI-MS (m/z, relative intensity): 249 (42), 233 (57), 191 (45), 165 (26), 73 (100); HRMS (ESI) calcd. for C 18 H 21 Si [(M+H) + ] 265.1407, found: 265.1411. (3-(Biphenyl-4-yl)prop-1-ynyl)trimethylsilane (3g) 1 H NMR (400 MHz, CDCl 3 ) δ 0.12 (s, 9H), 3.61 (s, 2H), 7.24 (t, J = 7.2 Hz, 1H), 7.31-7.36 (m, 4H), 7.45-7.51 (m, 4H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 26.0, 87.2, 104.4, 127.2, 127.3, 127.4, 128.5, 128.9, 135.7, 139.8, 141.1; IR (film) 2959, 2177, 1488, 1250, 1030, 842, 758 cm -1 ; EI-MS (m/z, relative intensity): 264 (M +, 79), 249 (100), 221 (38), 165 (15), 125 (17), 73 (32); HRMS (ESI) calcd. for C 18 H 21 Si [(M+H) + ] 265.1407, found: 265.1410. (3-(3,4-Dimethoxyphenyl)prop-1-ynyl)trimethylsilane (3h) 1 H NMR (400 MHz, CDCl3) δ 0.02 (s, 9H), 3.43 (s, 2H), 3.70 (s, 6H), 3.72 (s, 3H), 6.62-6.74 (m, 2H), 6.75 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 0.84, 21.8, 56.5, 56.7, 87.6, 105.5, 112.0, 112.1, 120.5, 129.6, 148.5, 149.7; IR (film) 2956, 2175, 1926, 1515, 1250, 843, 760 cm -1 ; EI-MS (m/z, relative intensity): 248 (M +, 100), 233 (82), 217 (17), 203 (21), 117 (14), 73 (32); HRMS (ESI) calcd. for C 14 H 19 O 2 Si [(M+H) + ] 179.0888, found: 179.0889. (3-(3,4-Dichlorophenyl)prop-1-ynyl)trimethylsilane (3i) 1 H NMR (400 MHz, CDCl 3 ) δ 0.03 (s, 9H), 3.42 (s, 2H), 7.00 (d, J = 6.4 Hz, 1H), 7.20 (d, J = 8.4 Hz, 1H), 7.26 (d, J = 1.6 Hz, Cl 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.81, 26.2, 88.9, 103.5, Cl 128.1, 130.7, 131.3, 131.5, 133.3, 137.4; IR (film) 2956, 2180, 1925, 1470, 1250, 1033, 842, 760 cm -1 ; EI-MS (m/z, relative intensity): 256 (M +, 21), 241 (100), 213 (16), 198 (16), 128 (14), 103 (15), 73 (14); HRMS (EI) calcd. for C 12 H 14 Cl 2 Si [M + ] 256.0242, found: 256.0245. S5
(E)-Methyl 3-(2-(3-(trimethylsilyl)prop-2-ynyl)phenyl)acrylate (3j) 1 H NMR (400 MHz, CDCl 3 ) δ 0.09 (s, 9H), 3.65 (s, 2H), CO 2 Me 3.74 (s, 3H), 7.20 (t, J = 7.2 Hz, 1H), 7.29 (t, J = 7.6 Hz, 1H), 7.42 (d, J = 7.6 Hz, 1H), 7.47 (d, J = 7.6 Hz, 1H), 7.93 (d, J = 16 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 24.8, 52.0, 86.4, 103.6, 120.2, 127.1, 127.7, 129.6, 130.6, 133.5, 135.9, 142.1, 167.5; IR (film) 2957, 2178, 1721, 1635, 1470, 1250, 1170, 842 cm -1 ; EI-MS (m/z, relative intensity): 271 (40), 257 (23), 229 (72), 185 (40), 140 (28), 89 (77), 73 (100), 59 (50); HRMS (ESI) calcd. for C 16 H 21 O 2 Si [(M+H) + ] 273.1305, found: 273.1309. Trimethyl(3-(2-(2-phenylethynyl)phenyl)prop-1-ynyl)silane (3k) 1 H NMR (400 MHz, CDCl 3 ) δ 0.12 (s, 9H), 3.84 (s, 2H), 7.14-7.18 (m, 1H), 7.25-7.29 (m, 4H), 7.41-7.49 (m, 3H), 7.54 (d, J = 7.6 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 25.4, 87.4, 87.7, 94.7, 103.9, 122.5, 123.4, 126.8, 128.1, 128.8, 128.8, 131.7, 132.0, 138.4; IR (film) 2989, 2178, 1494, 1250, 1026, 842, 754 cm -1 ; EI-MS (m/z, relative intensity): 288 (M +, 8), 273 (20), 215 (29), 137 (11), 73 (100); HRMS (ESI) calcd. for C 20 H 21 Si [(M+H) + ] 289.1407, found: 289.1409. 4-(2-(3-(Trimethylsilyl)prop-2-ynyl)phenyl)pyridine (3l) 1 H NMR (400 MHz, CDCl 3 ) δ 0.07 (s, 9H), 3.44 (s, 2H), 7.12-7.13 (m, 1H), 7.14-7.29 (m, 3H), 7.35 (dt, J = 8.0 Hz, J = 5.2 Hz, 1H), 7.54 (d, J = 7.6 Hz, 1H), 8.60 (d, J = 5.6 Hz, 2H); 13 C NMR (100 N MHz, CDCl 3 ) δ 0.77, 25.4, 88.1, 104.9, 125.1, 127.9, 129.7, 130.2, 130.3, 134.6, 139.4, 150.0, 150.4; IR (film) 2959, 2175, 1595, 1251, 1016, 843, 760 cm -1 ; EI-MS (m/z, relative intensity): 264 (31), 250 (100), 220 (6), 180 (13), 167 (7), 73 (16); HRMS (ESI) calcd. for C 17 H 20 NSi [(M+H) + ] 266.1360, found: 266.1361. (3-(2,4- Di-( p-methoxylphenyl)phenyl)prop-1-ynyl)trimethylsilane (3m) 1 H NMR (400 MHz, CDCl 3 ) δ 0.09 (s, 9H), 3.47 (s, 2H), 3.75 (d, J = 7.6 Hz, 4H), 6.87 (d, 8.8 Hz, 4H), 7.22 (d, J = 8.8 Hz, 2H), 7.33 (s, 1H), 7.44-7.47 (m, 3H), 7.56 (d, J = 8.0 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.81, 25.1, 56.0, 61.1, 87.3, 105.9, 114.4, 114.9, 126.3, 128.8, 129.1, 130.1, 131.0, 133.3, 134.0, 134.1, 140.0, 142.2, 159.6, 159.9; IR (film) 2957, 2175, 1610, 1516, 1248, 841, 760 cm -1 ; EI-MS (m/z, relative intensity): 328 (100), 313 (30), 297 (30), 239 (35), 207 (30), 119 (25); HRMS (ESI) calcd. for C 26 H 29 O 2 Si [(M+H) + ] 401.1931, found: 401.1935. S6
(3-(Furan-2-yl)prop-1-ynyl)trimethylsilane (3n) 1 H NMR (400 MHz, CDCl 3 ) δ 0.02 (s, 9H), 3.43 (s, 2H), 6.03-6.04 (m, 1H), 6.14-6.15 (m, 1H), 7.09-7.16 (m, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.90, 20.8, 87.3, 102.0, 107.1, 111.3, 142.6, 151.0; IR (film,) 2957, 2184, 1250, 1004, 843, 760 cm -1 ; EI-MS (m/z, relative intensity): 178 (M +, 47), 163 (100), 148 (11), 135 (10), 107 (9), 83 (13), 73 (31); HRMS (ESI) calcd. for C 10 H 15 OSi [(M+H) + ] 249.1305, found: 249.1308. Trimethyl(3-(2-(thiophen-2-yl)phenyl)prop-1-ynyl)silane (3o) 1 H NMR (400 MHz, CDCl 3 ) δ 0.09 (s, 9H), 3.62 (s, 2H), 7.00-7.01 (m, S 2H), 7.20 (t, J = 9.2 Hz, 1H), 7.27-7.31 (m, 3H), 7.55 (d, J = 7.0 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 25.2, 87.4, 104.9, 125.8, 127.0, 127.0, 127.4, 128.5, 131.1, 133.9, 135.0, 142.1; IR (film) 2958, 2176, 1483, 1250, 1020, 841, 759 cm -1 ; EI-MS (m/z, relative intensity): 270 (M +, 10), 255 (38), 239 (50), 197 (53), 165 (100), 73 (89); HRMS (ESI) calcd. for C 16 H 19 SSi [(M+H) + ] 271.0971, found: 271.0975. Trimethyl(3-phenylbut-1-ynyl)silane (6a) 4 Trimethyl(3-phenylpent-1-ynyl)silane (6b) 1 H NMR (400 MHz, CDCl 3 ) δ 0.11 (s, 9H), 1.41 (d, J = 7.2 Hz, 3H), 3.71 (q, J = 7.2 Hz, 1H), 7.16 (d, J = 8.4 Hz, 1H), 7.24 (m, 2H), 7.30 (d, J = 7.2 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 24.7, 32.9, 86.4, 109.6, 126.7, 127.0, 128.6, 143.2. 1 H NMR (400 MHz, CDCl 3 ) δ 0.11 (s, 9H), 0.91 (t, J = 7.2 Hz, 3H), 1.62-1.74 (m, 2H), 3.52 (t, J = 7.2 Hz, 1H), 7.12-7.16 (m, 1H), 7.21-7.27 (m, 4H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 11.7, 31.8, 40.4, 87.4, 108.4, 126.7, 127.6, 128.4, 141.8; IR (film) 2926, 2171, 1249, 841, 698, 668 cm -1 ; EI-MS (m/z, relative intensity): 216 (M +, 39); 201 (55); 187 (100). 159 (90), 83 (29), 73 (54); HRMS (ESI) calcd. for C 14 H 21 Si [(M+H) + ] 217.1407, found: 217.1407. (3-Cyclopropyl-3-phenylprop-1-ynyl)trimethylsilane (6c) 1 H NMR (400 MHz, CDCl 3 ) δ 0.10 (s, 9H), 0.38-0.46 (m, 4H), 1.00-1.08 (m, 1H), 3.48 (d, J = 6.4 Hz, 1H), 7.18 (d, J = 5.2 Hz, 1H), 7.25 (m, 2H), 7.33 (d, J = 7.3 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 2.9, 4.0, 17.3, 41.5, 87.5, 106.2, 127.6, 128.5, 141.9; IR (film) 2959, 2173, 1493, 1249, 840, 760, 698 cm -1 ; EI-MS (m/z, relative intensity): 213 (7), 200 (51), 185 (100), 159 (18), 104 (30), 73 (25); HRMS (ESI) calcd. for S7
C 15 H 21 Si [(M+H) + ] 229.1407, found: 229.1410. (3-(Benzo[d][1,3]dioxol-5-yl)hex-1-ynyl)trimethylsilane (6d) 1 H NMR (400 MHz, CDCl 3 ) δ 0.10 (s, 9H), 0.84 (t, J = 7.6 Hz, 3H), 1.30-1.40 (m, 2H), 1.53-1.63 (m, 2H), 3.49 (t, J = 7.2 Hz, 1H), 5.86 (s, 2H), 6.65-6.71 (m, 2H), 6.79 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 13.9, 20.5, 38.3, 41.0, 87.1, 101.0, 108.1, 108.1, 108.7, 120.6, 136.1, 146.3, 147.7; IR (film) 2960, 2170, 1504, 1487, 1249, 1041, 841, 760 cm -1 ; EI-MS (m/z, relative intensity): 274 (M +, 32), 259 (10), 231 (100), 216 (18), 203 (49), 108 (8), 73 (10); HRMS (ESI) calcd. for C 16 H 23 O 2 Si [(M+H) + ] 275.1462, found: 275.1464. Trimethyl(3-(naphthalen-2-yl)but-1-ynyl)silane (6e) 1 H NMR (400 MHz, CDCl 3 ) δ 0.12 (s, 9H), 1.48 (d, J = 7.2 Hz, 3H), 3.86 (q, J = 7.2 Hz, 1H), 7.35-7.43 (m, 3H), 7.71-7.73 (m, 4H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 24.4, 33.0, 86.6, 109.6, 125.2, 125.6, 125.6, 126.1, 127.7, 127.9, 128.3, 132.5, 133.6, 140.5; IR (film) 2959, 2166, 1250, 841, 746 cm -1 ; EI-MS (m/z, relative intensity): 252 (M +, 100), 237 (73), 209 (46), 197 (20), 178 (24), 111 (30), 73 (72); HRMS (ESI) calcd. for C 17 H 21 Si [(M+H) + ] 253.1407, found: 253.1408. (3-(3-Bromophenyl)but-1-ynyl)trimethylsilane (6f) 1 H NMR (400 MHz, CDCl 3 ) δ 0.11 (s, 9H), 1.39 (d, J = 7.2 Hz, 3H), 3.67 (q, J = 6.8 Hz, 1H), 7.10-7.13 (m, 1H), 7.22-7.29 (m, 2H), 7.45 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 24.5, 32.7, 87.2, 108.7, 122.7, 125.8, 129.9, 130.2, 130.3, 145.5; IR (film) 2857, 2169, 1594, 1477, 1249, 842, 760 cm -1 ; EI-MS (m/z, relative intensity): 281 ([M+1] +, 25), 280 (M +, 25), 267 (100), 237 (15), 128 (35), 83 (30), 73 (96); HRMS (EI) calcd. for C 13 H 17 BrSi [M + ] 280.0283, found: 280.0283. (3,3-Diphenylprop-1-ynyl)trimethylsilane (6g) 5 1 H NMR (400 MHz, CDCl 3 ) δ 0.13 (s, 9H), 4.94 (s, 1H), 7.12-7.16 (m, 2H), 7.22 (t, J = 7.6 Hz, 4H), 7.29 (d, J = 7.3 Hz, 4H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 44.3, 89.3, 106.9, 127.0, 128.0, 128.7, 141.7. S8
(3,3-Di-p-tolylprop-1-ynyl)trimethylsilane (6h) 1 H NMR (400 MHz, CDCl 3 ) δ 0.11 (s, 9H), 2.22 (s, 6H), 4.86 (s, 1H), 7.01 (d, J = 7.6 Hz, 4H), 7.16 (d, J = 7.6 Hz, 4H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 21.2, 43.5, 88.7, 107.3, 127.8, 129.4, 136.5, 139.0; IR (film) 2956, 2171, 1511, 1249, 1040, 843, 759 cm -1 ; EI-MS (m/z, relative intensity): 292 (M +, 37), 277 (26), 249 (18), 219 (19), 73 (100); HRMS (ESI) calcd. for C 20 H 25 Si [(M+H) + ] 293.1720, found: 293.1722. (3,3-Bis(4-fluorophenyl)prop-1-ynyl)trimethylsilane (6i) F 1 H NMR (400 MHz, CDCl 3 ) δ 0.11 (s, 9H), 4.87 (s, 1H), 6.89 (t, F J = 6.9 Hz, 4H), 7.20 (t, J = 7.2 Hz, 4H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.13, 42.7, 89.8, 106.2, 115.5 (d, J = 21.4 Hz), 129.4 (d, J = 8.1 Hz), 137.2 (d, J = 3.1 Hz), 161.9 (d, J = 244.1 Hz); IR (film) 2960, 2173, 1506, 1250, 1229, 840, 760 cm -1 ; EI-MS (m/z, relative intensity): 300 (M +, 10), 285 (27), 257 (28), 208 (100), 163 (16), 73 (42); HRMS (EI) calcd. for C 18 H 18 F 2 Si [M + ] 300.1146, found: 300.1145. (3-(3,4-Dimethylphenyl)-3-phenylprop-1-ynyl)trimethylsilane (6j) 1 H NMR (400 MHz, CDCl 3 ) δ 0.20 (s, 9H), 2.21 (d, J = 4.0 Hz, 6H), 4.94 (s, 1H), 7.04-7.12 (m, 3H), 7.19 (t, J = 7.2 Hz, 1H), 7.28 (t, J = 8.0 Hz, 2H), 7.37 (d, J = 7.2 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 19.5, 20.0, 43.9, 88.9, 107.3, 125.3, 126.8, 127.9, 128.7, 129.3, 130.0, 135.2, 136.8, 139.2, 142.0; IR (film) 2960, 2172, 1493, 1452, 1240, 841, 687 cm -1 ; EI-MS (m/z, relative intensity): 292 (M +, 23), 277 (17), 249 (10), 219 (11), 73 (100); HRMS (ESI) calcd. for C 20 H 25 Si [(M+H) + ] 293.1720, found: 293.1722. (3,3-Diphenylprop-1-ynyl)triisopropylsilane (6k) 1 H NMR (400 MHz, CDCl 3 ) δ 1.01 (s, 21H), 4.96 (s, 1H), 7.11 (t, J = 7.1 Hz, 2H), 7.20 (m, 4H), 7.32 (d, J = 7.3 Hz, 4H); 13 C NMR (100 MHz, CDCl 3 ) δ 10.3, 17.6, 43.3, 84.3, 107.4, 125.7, 126.8, 127.4, 140.8; IR (film) 2943, 2865, 2170, 1493, 1462, 883, 697 cm -1 ; EI-MS (m/z, relative intensity): 348 (M +, 5), 305 (100), 277 (15), 235 (23), 135 (19), 121 (27); HRMS (ESI) calcd. for C 24 H 33 Si [(M+H) + ] 349.2346, found: 349.2349. S9
(Chroman-4-ylethynyl)trimethylsilane (6l) O 1 H NMR (400 MHz, CDCl 3 ) δ 0.15 (s, 9H), 2.08-2.23 (m, 2H), 3.86 (t, J = 6.4 Hz, 1H), 4.16 (t, J = 8.4 Hz, 1H), 4.33 (t, J = 7.6 Hz, 1H), 6.79 (d, J = 8.0 Hz, 1H), 6.89 (t, J = 7.2 Hz, 1H), 7.13 (t, J = 7.6 Hz, 1H), 7.35 (d, J = 7.6 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.06, 28.4, 29.0, 64.3, 86.0, 107.9, 116.9,120.5,121.5, 128.3, 129.6, 135.7; IR (film, cm -1 ) 2960, 2170, 1488, 1250, 1225, 842, 752; EI-MS (m/z, relative intensity): 230 (96), 215.1 (27), 199.0 (19), 187.1 (73), 161.0 (24), 107.5 (19), 73.1 (100); ; HRMS (EI) calcd. for C 14 H 18 OSi [M + ] 230.1127, found: 230.1129. Trimethyl(5-phenylpent-1-ynyl)silane (6m) 6 Trimethyl(4-phenylbut-1-ynyl)silane (6n) 7 1 H NMR (400 MHz, CDCl 3 ) δ 0.09 (s, 9H), 1.72-1.79 (m, 2H), 2.15 (t, J = 6.8 Hz, 2H), 2.83 (t, J = 6.8 Hz, 2H), 7.09-7.11 (m, 3H), 7.20 (t, J = 7.2 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.17, 19.1, 30.0, 34.5, 84.8, 106.9, 125.6, 128.2, 128.3, 141.4. 1 H NMR (400 MHz, CDCl 3 ) δ 0.14 (s, 9H), 2.49 (t, J = 7.6 Hz, 2H), 2.82 (t, J = 7.6 Hz, 2H), 7.26-7.30 (m, 5H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 22.4, 35.3, 85.5, 106.9, 126.5, 128.5, 128.7, 140.8. (3-Cyclohexylprop-1-ynyl)trimethylsilane (6o) 8 106.6. 1 H NMR (400 MHz, CDCl 3 ) δ 0.15 (s, 9H), 0.93-1.02 (m, 2H), 1.11-1.29 (m, 4H), 1.64-1.81 (m, 5H), 2.11 (d, J = 6.8 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 26.2, 26.4, 27.7, 32.7, 37.4, 85.2, (5-(4-tert-Butylphenyl)-4-methylpent-1-ynyl)trimethylsilane (6p) 1 H NMR (400 MHz, CDCl 3 ) δ 0.09 (s, 9H), 0.92 (d, J = 6.4 Hz, 3H), 1.23 (s, 9H), 1.82-1.90 (m, 1H), 1.95-2.04 (m, 2H), 2.08-2.14 (m, 1H), 2.37-2.42 (m, 1H), 2.57-2.62 (m, 1H), 7.01 (d, J = 8.2 Hz, 2H), 7.21 (d, J = 8.2 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 19.5, 26.6, 31.5, 34.4, 34.8, 41.8, 86.0, 106.3, 125.1, 128.9, 137.6, 148.7; IR (film) 2959, 2174, 1515, 1249, 841, 759 cm -1 ; EI-MS (m/z, relative intensity): 286 (M +, 8), 271 923), 229 (26), 174 (62), 159 (100), 128 (30), 73 (48), 57 (21); HRMS (ESI) calcd. for C 19 H 31 Si [(M+H) + ] 287.2190, found: 287.2194. S10
(E)-Trimethyl(undec-4-en-1-ynyl)silane (6q) 1 H NMR (400 MHz, CDCl 3 ) δ 0.09 (s, 9H), 0.81 (t, J = 7.2 Hz, 3H), 1.21-1.29 (m, 8H), 1.92-1.97 (m, 2H), 2.87-2.91 (m, 2H), 5.28-5.38 (m, 1H), 5.57-5.64 (m, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.28, 14.2, 22.8, 23.2, 29.0, 29.4, 31.9, 32.4, 86.2, 105.0, 123.6, 132.7; IR (film) 2927, 2177, 1250, 842, 700 cm -1 ; EI-MS (m/z, relative intensity): 207 (80), 148 (10), 135 (12), 123 (14), 109 (27), 73 (100), 59 (46); HRMS (EI) calcd. for C 14 H 26 Si [M + ] 222.1804, found: 222.1804. (4,4-Dimethylpent-1-ynyl)triisopropylsilane (6r) 1 H NMR (400 MHz, CDCl 3 ) δ 0.93 (s, 9H), 1.00 (s, 21H), 2.05 (s, 2H); t Bu 13 C NMR (100 MHz, CDCl 3 ) δ 11.4, 18.7, 29.0, 31.2, 35.0, 81.5, 107.4; TIPS IR (film) 2943, 2966, 2172, 1464, 1019, 883, 676, 665 cm -1 ; EI-MS (m/z, relative intensity): 252 (M +, 6), 209 (100), 181 (30), 153 (49), 139 (61), 83 (18); HRMS (EI) calcd. for C 16 H 32 Si [M + ] 252.2273, found: 252.2278. Triisopropyl(4-methylpent-1-ynyl)silane (6s) 9 1 H NMR (400 MHz, CDCl 3 ) δ 0.95-0.98 (m, 3H), 1.02 (d, J = 1.0 Hz, 22H), 1.11 (d, J = 6.8 Hz, 1H), 2.28 (s, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 10.0, 17.4, 17.6, 22.2, 85.2, 93.7. Triisopropyl(3-methylhex-1-ynyl)silane (6t) 1 H NMR (400 MHz, CDCl 3 ) δ 0.82-0.86 (m, 3H), 0.91-1.05 (m, 25H), 1.09 (d, J = 6.8 Hz, 3H), 2.35-2.44 (m, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 11.3, 13.9, 18.6, 20.5, 21.3, 26.7, 39.3, 79.4, 114.1; IR (film) 2958, 2866, 2164, 1464, 883, 675, 661 cm -1 ; EI-MS (m/z, relative intensity): 223 (100), 195 (23), 181 (19), 167 (29), 153 (38); HRMS (EI) calcd. for C 16 H 32 Si [M + ] 252.2273, found: 252.2272. Triisopropyl(3,4,4-trimethylpent-1-ynyl)silane (6u) 1 H NMR (400 MHz, CDCl 3 ) δ 0.90-0.93 (m, 9H), 0.94-0.99 (m, 21H), 1.05 (d, J = 7.5 Hz, 3H), 2.20 (q, J = 6.8 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 11.4, 16.2, 18.7, 27.2, 33.2, 38.3, 80.7, 112.8; IR (film) 2943, 2866, 2172, 1464, 1019, 883, 676, 665 cm -1 ; EI-MS (m/z, relative intensity): 223 (27), 209 (100), 167 (50), 153 (33), 139 (30), 73 (42), 59 (41); HRMS (EI) calcd. for C 17 H 34 Si [M + ] 266.2430, found: 266.2435. S11
(3-Cyclopropylbut-1-ynyl)triisopropylsilane (6v) 1 H NMR (400 MHz, CDCl 3 ) δ 0.24-0.35 (m, 4H), 0.70-0.76 (m, 1H), 0.98-1.00 (m, 21H), 1.83 (d, J = 6.8 Hz, 3H), 2.35-2.42 (m, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 3.2, 11.3, 15.9, 18.6, 21.4, 29.9, 80.2, 110.9; IR (film) 2942, 2866, 2172, 1462, 1018, 882, 662 cm -1 ; EI-MS (m/z, relative intensity): 223 (27), 209 (100), 167 (50), 153 (33), 139 (30), 73 (42), 59 (41); HRMS (ESI) calcd. for C 16 H 31 Si [(M+H) + ] 251.2190, found: 251.2194. Trimethyl(tridec-12-en-1-ynyl)silane (6w) 1 H NMR (400 MHz, CDCl 3 ) δ 0.07 (s, 9H), 1.21-1.30 (m, 12H), 1.40-1.47 (m, 2H), 1.94-2.00 (m, 2H), 2.12-2.15 (m, 2H), 4.84-4.94 (m, 2H), 5.69-5.79 (m, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.17, 19.8, 28.6, 18.8, 18.9, 29.0, 29.1, 29.3, 29.4, 33.8, 84.2, 107.7, 114.1, 139.2; IR (film) 2943, 2865, 2170, 1462, 1018, 882, 676 cm -1 ; EI-MS (m/z, relative intensity): 154 (15), 139 (25), 125 (24), 109 (27), 99 (22), 73 (100), 59 (48); HRMS (EI) calcd. for C 16 H 30 Si [M + ] 250.2217, found: 250.2218. (Cyclohexylethynyl)triisopropylsilane (6x) 10 TIPS 1 H NMR (400 MHz, CDCl 3 ) δ 0.99-1.09 (m, 21H), 1.30-1.38 (m, 3H), 1.48 (t, J = 9.3 Hz, 3H), 1.74 (t, J = 11.2 Hz, 4H), 2.36-2.46 (m, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 11.3, 18.6, 24.5, 26.0, 29.9, 32.8, 79.5, 113.6. Trimethyl((4-phenylcyclohexyl)ethynyl)silane (6y) 1 H NMR (400 MHz, CDCl 3 ) δ 0.20 (s, 9H), 1.60 (t, J = 13.6 Hz, 2H), 1.73 (t, J = 10.8 Hz, 2H), 1.93-1.95 (m, 4H), 2.44-2.50 (m, 1H), 2.87 (s, 1H), 7.22-7.25 (m, 3H), 7.29-7.31 (m, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.31, 27.5, 29.5, 31.1, 44.2, 86.2, 110.5, 125.9, 126.8, 128.3, 147.6; IR (film, cm -1 ) 2932, 2857, 2166, 1250, 842, 699; EI-MS (m/z, relative intensity): 265.1 (23), 241.2 (100),228.1 (8), 182.1 (8), 159.1 (17), 135.1 (20), 83.1 (19), 73.1 (32); HRMS (EI) calcd. for C 17 H 24 Si [M + ] 256.1647, found: 256.1642. (Cyclopentylethynyl)triisopropylsilane (6z) TIPS 1 H NMR (400 MHz, CDCl 3 ) δ 1.05-1.09 (m, 21H), 1.55-1.59 (m, 2H), 1.61-1.67 (m, 2H), 1.70-1.74 (m, 2H), 2.63-2.70 (m, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 11.3, 18.6, 24.9, 31.2, 34.2, 86.2, 114.1; IR (film, S12
cm -1 ) 2943, 2865, 2172, 1463, 995, 883, 674; EI-MS (m/z, relative intensity): 250.2 (5), 207.2 (100), 179.1 (33), 165.1 (36), 151.1 (44), 137.1 (74), 109.1 (18), 59.1 (23); HRMS (EI) calcd. for C 16 H 30 Si [M + ] 250.2117, found: 250.2260. (Cyclohex-2-enylethynyl)triisopropylsilane (8) TIPS 1 H NMR (400 MHz, CDCl 3 ) δ 1.03-1.07 (m, 21H), 1.56-1.63 (m, 4H), 1.94-2.08 (m, 2H), 3.06-3.18 (m, 1H), 5.68 (q, J = 10.0 Hz, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 11.3, 18.7, 21.5, 22.3, 25.6, 29.3, 86.9, 109.4, 121.1, 135.5; IR (film, cm -1 ) 2941, 2864, 2172, 1732, 1463, 883, 676; EI-MS (m/z, relative intensity): 262 (7), 219.2 (100), 207.0 (9),191.1 (24), 177.1 (21), 163.1 (25), 149.1 (37), 83.0 (22), 59.0 (24); HRMS (EI) calcd. for C 17 H 30 NSi [M + ] 262.2117, found: 262.2112. (6,6-Dimethylhepta-3,4-dienyl)benzene (10) 11 142.0, 201.1. t Bu 1 H NMR (400 MHz, CDCl 3 ) δ 0.93 (s, 9H), 2.19-2.26 (m, 2H), 2.63 (t, J = 7.6 Hz, 2H), 5.01-5.04 (m, 1H), 5.10-5.14 (m, 1H), 7.07-7.12 (m, 3H), 7.17-7.21 (m, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 30.2, 30.9, 31.7, 35.5, 92.1, 103.5, 125.8, 128.3, 128.5, S13
7) References (1) Fulton, J.; Aggarwal, V.; de Vicente, J. Eur. J. Org. Chem. 2005, 8, 1479. (2) Aikawa, K.; Hioki, Y.; Mikami, K. Org. Lett. 2010, 12, 5716. (3) Biradar, D. B.; Gau, H. M. Chem. Commun. 2011, 47, 10467. (4) Sun, J.; Conley, M. P.; Zhang, L.; Kozmin, S. J. Am. Chem. Soc. 2006, 128, 9705. (5) Porter, N. A.; Hogenkamp, D. J.; Khouri, F. F. J. Am. Chem. Soc. 1990, 112, 2402. (6) Nakamura, M.; Ito, S.; Matsuo, K.; Nakamura, E. Synlett 2005, 1794. (7) Shimizu, K.; Takimoto, M.; Sato, Y.; Mori, M. Org. Lett. 2005, 7, 195. (8) Najdi, M. R.; Wang, M. L.; Zweifel, G. J. Org. Chem. 1991, 56, 2468. (9) Zhang, L.; Kozmin, S. J. Am. Chem. Soc. 2005, 127, 6962. (10) Xiang, J.; Fuchs, P. L. Tetrahedron Lett. 1998, 39, 8597. (11) Zhong, C.; Sasaki, Y.; Ito, H.; Sawamura, M. Chem. Commun. 2009, 5850. S14
8) 1 H NMR and 13 C NMR spectra Trimethyl(3-phenylprop-1-ynyl)silane (3a) S15
4-(3-(Trimethylsilyl)prop-2-ynyl)benzonitrile (3b) S16
Trimethyl(3-(3-nitrophenyl)prop-1-ynyl)silane (3c) S17
N,N-Dimethyl-4-(3-(trimethylsilyl)prop-2-ynyl)benzenamine (3d) S18
Trimethyl(3-(4-(4,4,6,6-tetramethyl-1,3,2-dioxaborinan-2-yl)phenyl)prop-1-ynyl)silane (3e) S19
(3-(Biphenyl-2-yl)prop-1-ynyl)trimethylsilane (3f) S20
(3-(Biphenyl-4-yl)prop-1-ynyl)trimethylsilane (3g) S21
(3-(3,4-Dimethoxyphenyl)prop-1-ynyl)trimethylsilane (3h) MeO OMe MeO OMe S22
(3-(3,4-Dichlorophenyl)prop-1-ynyl)trimethylsilane (3i) S23
(E)-Methyl 3-(2-(3-(trimethylsilyl)prop-2-ynyl)phenyl)acrylate (3j) CO 2 Me CO 2 Me S24
Trimethyl(3-(2-(2-phenylethynyl)phenyl)prop-1-ynyl)silane (3k) S25
4-(2-(3-(Trimethylsilyl)prop-2-ynyl)phenyl)pyridine (3l) S26
(3-(2,4- Di-( p-methoxylphenyl)phenyl)prop-1-ynyl)trimethylsilane (3m) MeO OMe MeO OMe S27
(3-(Furan-2-yl)prop-1-ynyl)trimethylsilane (3n) O S28
Trimethyl(3-(4-(thiophen-2-yl)phenyl)prop-1-ynyl)silane (3o) S29
Trimethyl(3-phenylbut-1-ynyl)silane (6a) S30
Trimethyl(3-phenylpent-1-ynyl)silane (6b) S31
(3-Cyclopropyl-3-phenylprop-1-ynyl)trimethylsilane (6c) S32
(3-(Benzo[d][1,3]dioxol-5-yl)hex-1-ynyl)trimethylsilane (6d) O O O O S33
Trimethyl(3-(naphthalen-2-yl)but-1-ynyl)silane (6e) S34
(3-(3-Bromophenyl)but-1-ynyl)trimethylsilane (6f) S35
(3,3-Diphenylprop-1-ynyl)trimethylsilane (6g) S36
(3,3-Di-p-tolylprop-1-ynyl)trimethylsilane (6h) S37
(3,3-Bis(4-fluorophenyl)prop-1-ynyl)trimethylsilane (6i) F F F F S38
(3-(3,4-Dimethylphenyl)-3-phenylprop-1-ynyl)trimethylsilane (6j) S39
(3,3-Diphenylprop-1-ynyl)triisopropylsilane (6k) TIPS S40
(Chroman-4-ylethynyl)trimethylsilane (6l) O O S41
Trimethyl(5-phenylpent-1-ynyl)silane (6m) S42
Trimethyl(4-phenylbut-1-ynyl)silane (6n) S43
(3-Cyclohexylprop-1-ynyl)trimethylsilane (6o) S44
(5-(4-tert-Butylphenyl)-4-methylpent-1-ynyl)trimethylsilane (6p) t Bu t Bu S45
(E)-Trimethyl(undec-4-en-1-ynyl)silane (6q) S46
(4,4-Dimethylpent-1-ynyl)triisopropylsilane (6r) S47
Triisopropyl(4-methylpent-1-ynyl)silane (6s) S48
Triisopropyl(3-methylhex-1-ynyl)silane (6t) TIPS TIPS S49
Triisopropyl(3,4,4-trimethylpent-1-ynyl)silane (6u) S50
(3-Cyclopropylbut-1-ynyl)triisopropylsilane (6v) S51
Trimethyl(tridec-12-en-1-ynyl)silane (6w) S52
(Cyclohexylethynyl)triisopropylsilane (6x) TIPS TIPS S53
Trimethyl((4-phenylcyclohexyl)ethynyl)silane (6y) S54
(Cyclopentylethynyl)triisopropylsilane (6z) TIPS TIPS S55
(Cyclohex-2-enylethynyl)triisopropylsilane (8) TIPS TIPS S56
(6,6-Dimethylhepta-3,4-dienyl)benzene (10) t Bu t Bu S57