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Enantioselective Synthesis of α,α-Disubstituted Cyclopentenes by an N-Heterocyclic Carbene-Catalyzed Desymmetrization of 1,3-Diketones
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Section:Abstract
The enantioselective synthesis of α,α-disubstituted cyclopentenes using N-heterocyclic carbene catalysis is reported. This desymmetrization reaction proceeds via a chiral enol generated in situ from the combination of an enantiopure azolium salt and α,β-unsaturated aldehyde. This reactive enol undergoes addition to one of two enantiotopic ketones to afford an optically active β-lactone after the intermediate carbinol is involved in an internal acylation event to release the carbene catalyst. In the substrates where R = aryl, a decarboxylation occurs immediately after lactone formation to produce the quaternary center-containing cyclopentene products in up to 96% ee. When the R group is alkyl, the β-lactones are isolated in moderate yield and high diastereo- and enantioselectivity.
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This article has been cited by 29 ACS Journal articles (5 most recent appear below).
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History
- Published In Issue August 22, 2007
- Received June 1, 2007
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