title: Stereospecific and Regioselective Isocyanide Insertions into Siliranes and Reactions of the Resulting Iminosilacyclobutanes.
abstract: The insertions of p-tolyl and tert-butyl isocyanide into siliranes yielded iminosilacyclobutanes with stereospecific retention of configuration. Monosubstituted siliranes underwent insertion into the more substituted Si-C bond of the ring, although this regioselectivity was eroded as substitution increased on the silirane ring. The iminosilacyclobutane products tautomerized thermally or in the presence of a palladium catalyst to yield the thermodynamically more stable aminosilacyclobutenes. Ring-expansion reactions of iminosilacyclobutanes were promoted by acids: treatment with aqueous copper sulfate produced an oxasilacyclopentane in high yield, whereas with trifluoroacetic acid, oxasilacyclohexanes were formed.
authors.affiliation: Department of Chemistry, University of California, Irvine, California 92697-2025.
authors.forename: Phuc T.
authors.initials: PT
authors.lastname: Nguyen
authors.forename: Wylie S.
authors.initials: WS
authors.lastname: Palmer
authors.forename: K. A.
authors.initials: KA
authors.lastname: Woerpel