Direct and enantioselective a-allylation of ketones via singly occupied molecular orbital (SOMO) catalysis

Anthony Mastracchio, Alexander A. Warkentin, Abbas M. Walji, David W.C. MacMillan

Research output: Contribution to journalArticlepeer-review

80 Scopus citations

Abstract

The first enantioselective organocatalytic a-allylation of cyclic ketones has been accomplished via singly occupied molecular orbital catalysis. Geometrically constrained radical cations, forged from the one-electron oxidation of transiently generated enamines, readily undergo allylic alkylation with a variety of commercially available allyl silanes. A reasonable latitude in both the ketone and allyl silane components is readily accommodated in this new transformation. Moreover, three new oxidatively stable imidazolidinone catalysts have been developed that allow cyclic ketones to successfully participate in this transformation. The new catalyst platform has also been exploited in the first catalytic enantioselective a-enolation and a-carbooxidation of ketones.

Original languageEnglish (US)
Pages (from-to)20648-20651
Number of pages4
JournalProceedings of the National Academy of Sciences of the United States of America
Volume107
Issue number48
DOIs
StatePublished - Nov 30 2010

All Science Journal Classification (ASJC) codes

  • General

Keywords

  • Asymmetric synthesis
  • Organocatalysis

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