SILICON CARBON UNSATURATED-COMPOUNDS .45. REACTION OF BENZOYLTRIS(TRIMETHYLSILYL)SILANE WITH ARYLLITHIUM REAGENTS

The reaction of benzoyltris(trimethylsilyl)silane (1) with phenyllithium in ether, followed by hydrolysis of the resulting mixture gave diphenylmethyl(trimethylsiloxy)bis(trimethylsilyl)silane and phenyl(diphenylmethyl)bis(trimethylsilyl)silane in 30% and 9% yields. Treatment of 1 with (o-tolyl)lithium afforded (phenyl(o-tolyl)methyl)(trimethylsiloxy)bis(trimethylsilyl)silane and (phenyl(o-tolyl)methyl)(o-tolyl)bis(trimethylsilyl)silane (3b) in 16% and 27% yields, while with (p-xylyl)lithium, 1 produced (phenyl(p-xylyl)methyl)(trimethylsiloxy)bis(trimethylsilyl)silane and (phenyl(p-xylyl)methyl)bis(trimethylsilyl)(p-xylyl)silane (3c) in 18% and 30% yields, respectively. The reaction of 1 with phenyllithium in the presence of 2,3-dimethylbutadiene produced 4,5-dimethyl-2,2-diphenyl-1,1-bis(trimethylsilyl)-1-silacyclohex-4-ene in 76% yield. Similar reaction of 1 with (o-tolyl)lithium in the presence of 2,3-dimethylbutadiene afforded 4,5-dimethyl-2-phenyl-2-(o-tolyl)-1,1-bis(trimethylsilyl)-1-silacyclohex-4-ene and 3b in 49 and 6% yields. With (p-xylyl)lithium, 1 gave a Diels-Alder cycloadduct and 3c in 47% and 26% yields, respectively.