Direct and enantioselective {alpha}-allylation of ketones via singly occupied molecular orbital (SOMO) catalysis.
basic_science · Level V
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- Record sourced from PubMed, PMID 20921367.
- Also identified by DOI 10.1073/pnas.1002845107 and PMC identifier 2996445.
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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.