Medium-Ring Effects on the Endo/Exo Selectivity of the Organocatalytic Intramolecular Diels-Alder Reaction

Joel F. Hooper, Natalie C. James, Esra Bozkurt, Viktorya Aviyente, Jonathan M. White, Mareike C. Holland, Ryan Gilmour, Andrew Bruce Holmes, K. N. Houk

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Abstract

The intramolecular Diels-Alder reaction has been used as a powerful method to access the tricyclic core of the eunicellin natural products from a number of 9-membered-ring precursors. The endo/exo selectivity of this reaction can be controlled through a remarkable organocatalytic approach, employing MacMillan's imidazolidinone catalysts, although the mechanistic origin of this selectivity remains unclear. We present a combined experimental and density functional theory investigation, providing insight into the effects of medium-ring constraints on the organocatalyzed intramolecular Diels-Alder reaction to form the isobenzofuran core of the eunicellins.

Original languageEnglish
Pages (from-to)12058-12075
Number of pages18
JournalThe Journal of Organic Chemistry
Volume80
Issue number24
DOIs
Publication statusPublished - 11 Nov 2015
Externally publishedYes

Keywords

  • Anthozoa
  • gorgonian coral
  • Diterpenes

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