Development of a generic activation mode: Nucleophilic α-substitution of ketones via oxy-allyl cations

Mark N. Vander Wal, Andrew K. Dilger, David W.C. MacMillan

Research output: Contribution to journalArticle

58 Scopus citations

Abstract

Oxy-allyl cations have been known as transient electrophilic species since they were first proposed as intermediates in the Favorskii rearrangement in 1894. Since that time, they also have been used as a mode of activation for [4 + 3] cycloadditions in a variety of natural product syntheses. In this manuscript, we describe a method for the interception of oxy-allyl cations with a diverse range of common nucleophiles, thereby demonstrating the value of this intermediate as a generic mode of activation. This simple, mild, room temperature protocol allows for the formation of a variety of high value carbon–carbon and carbon–heteroatom bonds that are readily incorporated within a series of cyclic and acyclic ketone systems. Initial efforts into the development of an enantioselective catalytic variant are also described.

Original languageEnglish (US)
Pages (from-to)3075-3079
Number of pages5
JournalChemical Science
Volume4
Issue number8
DOIs
StatePublished - Jul 1 2013

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

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