Tandem Base-Promoted Ring-Opening/Brook Rearrangement/Allylic Alkylation of O-Silyl Cyanohydrins of β-Silyl-α,β-epoxyaldehyde: Scope and Mechanism

Michiko Sasaki, Eiji Kawanishi, Yoshio Nakai, Tatsuya Matsumoto, Kentaro Yamaguchi, Kei Takeda

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32 Citations (Scopus)


Metalated O-silyl cyanohydrins of β-silyl-α,β -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.

Original languageEnglish
Pages (from-to)9330-9339
Number of pages10
JournalJournal of Organic Chemistry
Issue number24
Publication statusPublished - Nov 28 2003
Externally publishedYes


All Science Journal Classification (ASJC) codes

  • Organic Chemistry

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