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

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 wit...

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Bibliographic Details
Published in:Proceedings of the National Academy of Sciences - PNAS 2010-11, Vol.107 (48), p.20648-20651
Main Authors: Mastracchio, Anthony, Warkentin, Alexander A, Walji, Abbas M, MacMillan, David W.C
Format: Article
Language:English
Subjects:
Aldehydes
Alkylation
Amines
Carbonates
Catalysis
Catalysts
Ketones
Molecular orbitals
Oxidation
Physical Sciences
Silanes
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Summary: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.
ISSN:0027-8424
1091-6490
DOI:10.1073/pnas.1002845107