title: Tandem base-promoted ring-opening/Brook rearrangement/allylic alkylation of O-silyl cyanohydrins of beta-silyl-alpha,beta-epoxyaldehyde: scope and mechanism.
abstract: Metalated O-silyl cyanohydrins of beta-silyl-alpha,beta-epoxyaldehyde have been found to serve as functionalized homoenolate equivalents by a tandem sequence involving base-promoted ring opening of the epoxide, Brook rearrangement, and alkylation of the resulting allylic anion. On the basis of mechanistic studies involving competitive experiments using the diastereomeric cyanohydrins, we propose a reaction pathway involving a silicate intermediate 36 formed by a concerted process via an anti-opening of the epoxide followed by the formation of an O-Si bond.
authors: Department of Synthetic Organic Chemistry, Graduate School of Medical Sciences, Hiroshima University, 1-2-3 Kasumi, Minami-Ku, Hiroshima 734-8551, Japan.
authors: Michiko
authors: M
authors: Sasaki
authors: Eiji
authors: E
authors: Kawanishi
authors: Yoshio
authors: Y
authors: Nakai
authors: Tatsuya
authors: T
authors: Matsumoto
authors: Kentaro
authors: K
authors: Yamaguchi
authors: Kei
authors: K
authors: Takeda