Oxidative heck vinylation for the synthesis of complex dienes and polyenes

Jared H. Delcamp, Paul E. Gormisky, M. Christina White

Research output: Contribution to journalArticle

Abstract

We introduce an oxidative Heck reaction for selective complex diene and polyene formation. The reaction proceeds via oxidative Pd(II)/sulfoxide catalysis that retards palladium-hydride isomerizations which previously limited the Heck manifold's capacity for furnishing stereodefined conjugated dienes. Limiting quantities of nonactivated terminal olefins (1 equiv) and slight excesses of vinyl boronic esters (1.5 equiv) that feature diverse functionality can be used to furnish complex dienes and polyenes in good yields and excellent selectivities (generally E:Z = >20:1; internal:terminal = >20:1). Because this reaction only requires prior activation of a single vinylic carbon, improvements in efficiency are observed for synthetic sequences relative to ones featuring reactions that require activation of both coupling partners.

Original languageEnglish (US)
Pages (from-to)8460-8463
Number of pages4
JournalJournal of the American Chemical Society
Volume135
Issue number23
DOIs
StatePublished - Jun 12 2013

ASJC Scopus subject areas

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

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