Photolysis of Organopolysilanes. Reaction of Trimethylsilylphenylsilylene with Functional-Group-Substituted Olefins

Article abstract of DOI:10.1021/ja00404a032

The photolysis of tris(trimethylsilyl)phenylsilane (1) in the presence of vinyl chloride or 1-bromo-2-methylpropene afforded, probably via silacyclopropane intermediates, the respective 1-alkenyl-1-halo-1-phenyltrimethyldisilanes in moderate yields.Photolysis of 1 in the presence of cis- and trans-1-chloropropene proceeded with high stereospecificity to give cis- and trans-1-(chlorodisilanyl)propene, respectively.Irradiation of 1 in the presence of ethyl vinyl ether afforded 1-methoxy-1-phenyl-1-vinyltrimethyldisilane after methanolysis of the photolysis product.Similar irradiation of 1 in the presence of ethyl vinyl ether, followed by treatment with hydrogen chloride, gave 1-chloro-1-(1'-ethoxyethyl)-1-phenyltrimethyldisilane and 1-chloro-1-(2'-ethoxyethyl)-1-phenyltrimethyldisilane.Irradiation of 1 with cis- and trans-1-methoxy-1-hexene, followed by ethanolysis, produced the corresponding cis- and trans-1-(ethoxydisilanyl)-1-hexene with high stereospesificity.Irradiation of 1 with vinyl acetate gave directly 1-acetoxy-1-phenyl-1-vinyltrimethyldisilane.