C(sp)-C(sp 3 ) Bond Formation through Cu-Catalyzed Cross-Coupling of N-Tosylhydrazones and Trialkylsilylethyne

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1 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 , China State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai , China 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

2 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, 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 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

3 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, 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

4 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), (m, 2H), (m, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ 0.87, 26.9, 87.7, 105.1, 127.3, 128.6, 129.2, (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, 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) + ] , found: 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) + ] , found: 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 + ] , found: S4

5 (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), (m, 1H), (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) + ] , found: (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), (m, 4H), (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) + ] , found: (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), (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) + ] , found: (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 + ] , found: S5

6 (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) + ] , found: 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), (m, 1H), (m, 4H), (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) + ] , found: (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), (m, 1H), (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) + ] , found: (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), (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) + ] , found: S6

7 (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), (m, 1H), (m, 1H), (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) + ] , found: 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), (m, S 2H), 7.20 (t, J = 9.2 Hz, 1H), (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) + ] , found: 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, H NMR (400 MHz, CDCl 3 ) δ 0.11 (s, 9H), 0.91 (t, J = 7.2 Hz, 3H), (m, 2H), 3.52 (t, J = 7.2 Hz, 1H), (m, 1H), (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) + ] , found: (3-Cyclopropyl-3-phenylprop-1-ynyl)trimethylsilane (6c) 1 H NMR (400 MHz, CDCl 3 ) δ 0.10 (s, 9H), (m, 4H), (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

8 C 15 H 21 Si [(M+H) + ] , found: (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), (m, 2H), (m, 2H), 3.49 (t, J = 7.2 Hz, 1H), 5.86 (s, 2H), (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) + ] , found: 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), (m, 3H), (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) + ] , found: (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), (m, 1H), (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 + ] , found: (3,3-Diphenylprop-1-ynyl)trimethylsilane (6g) 5 1 H NMR (400 MHz, CDCl 3 ) δ 0.13 (s, 9H), 4.94 (s, 1H), (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, S8

9 (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) + ] , found: (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, (d, J = 21.4 Hz), (d, J = 8.1 Hz), (d, J = 3.1 Hz), (d, J = 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 + ] , found: (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), (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) + ] , found: (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) + ] , found: S9

10 (Chroman-4-ylethynyl)trimethylsilane (6l) O 1 H NMR (400 MHz, CDCl 3 ) δ 0.15 (s, 9H), (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), (27), (19), (73), (24), (19), 73.1 (100); ; HRMS (EI) calcd. for C 14 H 18 OSi [M + ] , found: 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), (m, 2H), 2.15 (t, J = 6.8 Hz, 2H), 2.83 (t, J = 6.8 Hz, 2H), (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, 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), (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, (3-Cyclohexylprop-1-ynyl)trimethylsilane (6o) H NMR (400 MHz, CDCl 3 ) δ 0.15 (s, 9H), (m, 2H), (m, 4H), (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), (m, 1H), (m, 2H), (m, 1H), (m, 1H), (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), ), 229 (26), 174 (62), 159 (100), 128 (30), 73 (48), 57 (21); HRMS (ESI) calcd. for C 19 H 31 Si [(M+H) + ] , found: S10

11 (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), (m, 8H), (m, 2H), (m, 2H), (m, 1H), (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 + ] , found: (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 + ] , found: Triisopropyl(4-methylpent-1-ynyl)silane (6s) 9 1 H NMR (400 MHz, CDCl 3 ) δ (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, Triisopropyl(3-methylhex-1-ynyl)silane (6t) 1 H NMR (400 MHz, CDCl 3 ) δ (m, 3H), (m, 25H), 1.09 (d, J = 6.8 Hz, 3H), (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 + ] , found: Triisopropyl(3,4,4-trimethylpent-1-ynyl)silane (6u) 1 H NMR (400 MHz, CDCl 3 ) δ (m, 9H), (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 + ] , found: S11

12 (3-Cyclopropylbut-1-ynyl)triisopropylsilane (6v) 1 H NMR (400 MHz, CDCl 3 ) δ (m, 4H), (m, 1H), (m, 21H), 1.83 (d, J = 6.8 Hz, 3H), (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) + ] , found: Trimethyl(tridec-12-en-1-ynyl)silane (6w) 1 H NMR (400 MHz, CDCl 3 ) δ 0.07 (s, 9H), (m, 12H), (m, 2H), (m, 2H), (m, 2H), (m, 2H), (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 + ] , found: (Cyclohexylethynyl)triisopropylsilane (6x) 10 TIPS 1 H NMR (400 MHz, CDCl 3 ) δ (m, 21H), (m, 3H), 1.48 (t, J = 9.3 Hz, 3H), 1.74 (t, J = 11.2 Hz, 4H), (m, 1H); 13 C NMR (100 MHz, CDCl 3 ) δ 11.3, 18.6, 24.5, 26.0, 29.9, 32.8, 79.5, 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), (m, 4H), (m, 1H), 2.87 (s, 1H), (m, 3H), (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): (23), (100),228.1 (8), (8), (17), (20), 83.1 (19), 73.1 (32); HRMS (EI) calcd. for C 17 H 24 Si [M + ] , found: (Cyclopentylethynyl)triisopropylsilane (6z) TIPS 1 H NMR (400 MHz, CDCl 3 ) δ (m, 21H), (m, 2H), (m, 2H), (m, 2H), (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

13 cm -1 ) 2943, 2865, 2172, 1463, 995, 883, 674; EI-MS (m/z, relative intensity): (5), (100), (33), (36), (44), (74), (18), 59.1 (23); HRMS (EI) calcd. for C 16 H 30 Si [M + ] , found: (Cyclohex-2-enylethynyl)triisopropylsilane (8) TIPS 1 H NMR (400 MHz, CDCl 3 ) δ (m, 21H), (m, 4H), (m, 2H), (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), (100), (9),191.1 (24), (21), (25), (37), 83.0 (22), 59.0 (24); HRMS (EI) calcd. for C 17 H 30 NSi [M + ] , found: (6,6-Dimethylhepta-3,4-dienyl)benzene (10) , t Bu 1 H NMR (400 MHz, CDCl 3 ) δ 0.93 (s, 9H), (m, 2H), 2.63 (t, J = 7.6 Hz, 2H), (m, 1H), (m, 1H), (m, 3H), (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

14 7) References (1) Fulton, J.; Aggarwal, V.; de Vicente, J. Eur. J. Org. Chem. 2005, 8, (2) Aikawa, K.; Hioki, Y.; Mikami, K. Org. Lett. 2010, 12, (3) Biradar, D. B.; Gau, H. M. Chem. Commun. 2011, 47, (4) Sun, J.; Conley, M. P.; Zhang, L.; Kozmin, S. J. Am. Chem. Soc. 2006, 128, (5) Porter, N. A.; Hogenkamp, D. J.; Khouri, F. F. J. Am. Chem. Soc. 1990, 112, (6) Nakamura, M.; Ito, S.; Matsuo, K.; Nakamura, E. Synlett 2005, (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, (9) Zhang, L.; Kozmin, S. J. Am. Chem. Soc. 2005, 127, (10) Xiang, J.; Fuchs, P. L. Tetrahedron Lett. 1998, 39, (11) Zhong, C.; Sasaki, Y.; Ito, H.; Sawamura, M. Chem. Commun. 2009, S14

15 8) 1 H NMR and 13 C NMR spectra Trimethyl(3-phenylprop-1-ynyl)silane (3a) S15

16 4-(3-(Trimethylsilyl)prop-2-ynyl)benzonitrile (3b) S16

17 Trimethyl(3-(3-nitrophenyl)prop-1-ynyl)silane (3c) S17

18 N,N-Dimethyl-4-(3-(trimethylsilyl)prop-2-ynyl)benzenamine (3d) S18

19 Trimethyl(3-(4-(4,4,6,6-tetramethyl-1,3,2-dioxaborinan-2-yl)phenyl)prop-1-ynyl)silane (3e) S19

20 (3-(Biphenyl-2-yl)prop-1-ynyl)trimethylsilane (3f) S20

21 (3-(Biphenyl-4-yl)prop-1-ynyl)trimethylsilane (3g) S21

22 (3-(3,4-Dimethoxyphenyl)prop-1-ynyl)trimethylsilane (3h) MeO OMe MeO OMe S22

23 (3-(3,4-Dichlorophenyl)prop-1-ynyl)trimethylsilane (3i) S23

24 (E)-Methyl 3-(2-(3-(trimethylsilyl)prop-2-ynyl)phenyl)acrylate (3j) CO 2 Me CO 2 Me S24

25 Trimethyl(3-(2-(2-phenylethynyl)phenyl)prop-1-ynyl)silane (3k) S25

26 4-(2-(3-(Trimethylsilyl)prop-2-ynyl)phenyl)pyridine (3l) S26

27 (3-(2,4- Di-( p-methoxylphenyl)phenyl)prop-1-ynyl)trimethylsilane (3m) MeO OMe MeO OMe S27

28 (3-(Furan-2-yl)prop-1-ynyl)trimethylsilane (3n) O S28

29 Trimethyl(3-(4-(thiophen-2-yl)phenyl)prop-1-ynyl)silane (3o) S29

30 Trimethyl(3-phenylbut-1-ynyl)silane (6a) S30

31 Trimethyl(3-phenylpent-1-ynyl)silane (6b) S31

32 (3-Cyclopropyl-3-phenylprop-1-ynyl)trimethylsilane (6c) S32

33 (3-(Benzo[d][1,3]dioxol-5-yl)hex-1-ynyl)trimethylsilane (6d) O O O O S33

34 Trimethyl(3-(naphthalen-2-yl)but-1-ynyl)silane (6e) S34

35 (3-(3-Bromophenyl)but-1-ynyl)trimethylsilane (6f) S35

36 (3,3-Diphenylprop-1-ynyl)trimethylsilane (6g) S36

37 (3,3-Di-p-tolylprop-1-ynyl)trimethylsilane (6h) S37

38 (3,3-Bis(4-fluorophenyl)prop-1-ynyl)trimethylsilane (6i) F F F F S38

39 (3-(3,4-Dimethylphenyl)-3-phenylprop-1-ynyl)trimethylsilane (6j) S39

40 (3,3-Diphenylprop-1-ynyl)triisopropylsilane (6k) TIPS S40

41 (Chroman-4-ylethynyl)trimethylsilane (6l) O O S41

42 Trimethyl(5-phenylpent-1-ynyl)silane (6m) S42

43 Trimethyl(4-phenylbut-1-ynyl)silane (6n) S43

44 (3-Cyclohexylprop-1-ynyl)trimethylsilane (6o) S44

45 (5-(4-tert-Butylphenyl)-4-methylpent-1-ynyl)trimethylsilane (6p) t Bu t Bu S45

46 (E)-Trimethyl(undec-4-en-1-ynyl)silane (6q) S46

47 (4,4-Dimethylpent-1-ynyl)triisopropylsilane (6r) S47

48 Triisopropyl(4-methylpent-1-ynyl)silane (6s) S48

49 Triisopropyl(3-methylhex-1-ynyl)silane (6t) TIPS TIPS S49

50 Triisopropyl(3,4,4-trimethylpent-1-ynyl)silane (6u) S50

51 (3-Cyclopropylbut-1-ynyl)triisopropylsilane (6v) S51

52 Trimethyl(tridec-12-en-1-ynyl)silane (6w) S52

53 (Cyclohexylethynyl)triisopropylsilane (6x) TIPS TIPS S53

54 Trimethyl((4-phenylcyclohexyl)ethynyl)silane (6y) S54

55 (Cyclopentylethynyl)triisopropylsilane (6z) TIPS TIPS S55

56 (Cyclohex-2-enylethynyl)triisopropylsilane (8) TIPS TIPS S56

57 (6,6-Dimethylhepta-3,4-dienyl)benzene (10) t Bu t Bu S57