Asymmetric boronate addition to o -quinone methides: Ligand exchange, solvent effects, and Lewis acid catalysis

Matthew N. Grayson, Jonathan M. Goodman

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

Density functional theory calculations suggest that asymmetric boronate addition to o-quinone methides proceeds via a Lewis acid catalyzed process through a closed six-membered transition structure. The BINOL-derived catalyst undergoes an exchange process with the original ethoxide boronate ligands. This activation mode successfully accounts for the sense and level of enantioselectivity observed experimentally. A qualitative model which accurately predicts the observed enantioselectivity has been developed and is consistent with results from our study of ketone propargylation demonstrating the reaction models generality. The effects of replacing the BINOL framework with H8-BINOL have been rationalized.

Original languageEnglish
Pages (from-to)2056-2061
Number of pages6
JournalJournal of Organic Chemistry
Volume80
Issue number4
Early online date28 Jan 2015
DOIs
Publication statusPublished - 20 Feb 2015

ASJC Scopus subject areas

  • Organic Chemistry
  • Medicine(all)

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