Rearrangement of Hydroxylated Pinene Derivatives to Fenchone-Type Frameworks: Computational Evidence for Dynamically-Controlled Selectivity

Marcus Blümel, Shota Nagasawa, Katherine Blackford, Stephanie R. Hare, Dean J. Tantillo, Richmond Sarpong

Research output: Contribution to journalArticlepeer-review

10 Citations (Scopus)

Abstract

An acid-catalyzed Prins/semipinacol rearrangement cascade reaction of hydroxylated pinene derivatives that leads to tricyclic fenchone-type scaffolds in very high yields and diastereoselectivity has been developed. Quantum chemical analysis of the selectivity-determining step provides support for the existence of an extremely flat potential energy surface around the transition state structure. This transition state structure appears to be ambimodal, i.e., the fenchone-type tricyclic scaffolds are formed in preference to the competing formation of a bornyl (camphor-type) skeleton under dynamic control via a post-transition state bifurcation (PTSB).

Original languageEnglish
Pages (from-to)9291-9298
Number of pages8
JournalJournal of the American Chemical Society
Volume140
Issue number29
DOIs
Publication statusPublished - 2018 Jul 25
Externally publishedYes

ASJC Scopus subject areas

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

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