Direct and enantioselective {alpha}-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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Published inProceedings of the National Academy of Sciences - PNAS Vol. 107; no. 48; pp. 20648 - 20651
Main Authors Mastracchio, Anthony, Warkentin, Alexander A, Walji, Abbas M, MacMillan, David W C
Format Journal Article
LanguageEnglish
Published United States National Academy of Sciences 30.11.2010
Subjects
Catalysis
Catalysts
Chemical reactions
Molecular chemistry
Organic chemicals
Oxidation
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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.
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ISSN:0027-8424
1091-6490
DOI:10.1073/pnas.1002845107