Tandem base-promoted ring-opening/Brook rearrangement/allylic alkylation of O-silyl cyanohydrins of beta-silyl-alpha,beta-epoxyaldehyde: scope and mechanism |
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Authors: | Sasaki Michiko Kawanishi Eiji Nakai Yoshio Matsumoto Tatsuya Yamaguchi Kentaro Takeda Kei |
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Affiliation: | Department of Synthetic Organic Chemistry, Graduate School of Medical Sciences, Hiroshima University, 1-2-3 Kasumi, Minami-Ku, Hiroshima 734-8551, Japan. |
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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. |
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