Zinc-Catalyzed β-Functionalization of Cyclopropanols via Enolized Homoenolate

Yoshiya Sekiguchi, Naohiko Yoshikai

Research output: Contribution to journalArticlepeer-review

Abstract

We report herein a zinc-catalyzed β-allylation of cyclopropanols with Morita-Baylis-Hillman (MBH) carbonates with retention of the cyclopropane ring. The reaction is promoted by a zinc aminoalkoxide catalyst, affording cyclopropyl-fused α-alkylidene-δ-valerolactone derivatives in moderate to good yields. Mechanistic experiments suggest that the present reaction does not proceed via direct β-C-H cleavage of the cyclopropanol, but involves zinc homoenolate and its enolization to generate a key bis-nucleophilic species. α-Allylation of this "enolized homoenolate"with MBH carbonate would be followed by regeneration of the cyclopropane ring and irreversible lactonization. The enolized homoenolate mechanism has also been proven to allow for β-functionalization with alkylidenemalononitrile as the reaction partner. A sequence of the present reaction and known cyclopropanol transformation provides an opportunity to transform a simple cyclopropanol into α,β- or β,β-difunctionalized ketones.

Original languageEnglish
Pages (from-to)18400-18405
Number of pages6
JournalJournal of the American Chemical Society
Volume143
Issue number44
DOIs
Publication statusPublished - 2021 Nov 10

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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