Work

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

Year: 2010

Type: article

Abstract: The first enantioselective organocatalytic α-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 α-enolation and α-carbooxidation of ketones.

Source: Proceedings of the National Academy of Sciences

DOI: 10.1073/pnas.1002845107

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

Institution: Princeton University

Language: English

Topic: Asymmetric Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funder: National Institute of General Medical Sciences

Awards: New Strategies in Metallaphotoredox Catalysis, G7747101108