Controlled introduction of allylic group to chlorosilanes

Selective mono- and di-allylation and allenylation of chlorosilanes using indium

“…Diallylmethylphenylsilane (5a) [9] IR: m max (liquid film) 3072. 5, 2971.3, 2916.2, 1630.0, 1426.9, 1252.1, 1154.2, 1113.2 cm À1 ; 1 H NMR (400 MHz,m,ArH),m,2 Â CH), (4H, m, 2 Â CH 2 @), 1.79-1.81 (4H, d, J = 7.1 Hz, 2 Â CH 2 CH@CH 2 ), 0.28 (3H, s, CH 3 ); 13 C NMR (100 MHz,CDCl 3 ): d 136.71,134.05,133.79,129.06,127.62,113.73,21.44,À5.98; MS: m/z (%): 202 (M + , 2.1), 161 (100), 121 (30.5), 105 (11.9).…”

“…Diallyldiphenylsilane ( 5b) [9] IR: m max (liquid film) 3069. 6, 2998.2, 1629.9, 1427.9, 1110.8, 907.9, 732.7 : d 134.84, 134.12, 133.55, 129.32, 127.65, 114.59, 19.85 : d 134.84,134.12,133.55,129.32,127.65,114.59,19.85;MS: m/z (%): 188 (M + , 2.31), 147 (100).…”

“…Diallylmethylbutylsilane (5e) [9]: 1 H NMR (400 MHz, CDCl 3 ): m,2 Â CH), (4H, m, 2 Â CH 2 @), 1.31-1.42 (8H, m), 0.92-1.07 (2H, m, CH 2 CH 3 ), 0.52-0.68 (3H, t, CH 3 CH 2 ), 0.21 (3H, s, CH 3 Si); 13 C NMR (100 MHz,CDCl 3 ): d 133.89,115.13,32.13,30.24,25.62,19.76,15.32,À2.67 Di-(2-methylbut-3-en-2-yl)methylphenylsilane ( 5f): 1 H NMR (400 MHz, CDCl 3 ): m,ArH),m,2 Â CH), (4H, m, 2 Â CH 2 @), 1.21 (12H, s, 4 Â CH 3 ), 0.31 (3H, s, CH 3 Si); 13 C NMR (100 MHz,CDCl 3 ): d 138.35,135.02,134.13,130.35,128.98 114.13,23.67,2.92 Si: C,79.00;H,10.14;Si,10.87. Found: C,78.88;H,10.82 Si, 01, 134.32, 133.87, 133.15, 130.78, 129.15, 115.11, 20.23, 17.23, À2.56; MS: m/z (%): 230 (M + , 0.56), 215 (3.24), 175 (100), 120 (65.32); Anal.…”

“…Allylchloromethylphenylsilane ( 6a) [9] IR: m max (liquid film) 3071. 2, 2969.5, 1630.5, 1427.8, 1256.2, 1157.0, 1118.3 (100), 181 (13.60).…”

“…These methods are useful for the preparation of novel and well-known silicon-containing alkenes, but it did not work well for synthesis of unsaturated chlorosilanes [7,8]. We previously found that allylsamarium bromide was a versatile reagent for the allylation of chlorosilanes with allyl bromide, but when RCH@CHCH 2 Br or 3-bromoprop-1-yne was used, this method failed [9]. Herein we reported the organoindium mediated selective mono-and di-allylation and allenylation of chlorosilanes into allylsilanes and allenylsilanes.…”