Anti-addition of Dimethylsulfoxonium Methylide to Acyclic α,β-Unsaturated Ketones and Its Application in Formal Synthesis of an Eicosanoid.

ABSTRACT: Cyclopropanation using dimethylsulfoxonium methylide (Corey-Chaykovsky reaction) was examined with a series of linear α,β-unsaturated ketones, and the results showed that the major trajectory for the addition of the sulfur ylide to the enones is anti, related to the γ-substituent. The stereochemical assignment for the generated cyclopropanes was achieved by X-ray crystallography or comparing with the reported spectroscopic data. We found that the diastereoselectivity was influenced by several factors, including the protecting groups, solvents, and temperatures, and good anti/syn ratios (>10:1) were often obtained using the tert-butyldimethylsilyl and tert-butyldiphenylsilyl-protected substrates. The method was applied to a formal synthesis of a natural eicosanoid with good ef

SUBMITTER: Angamuthu V 

PROVIDER: S-EPMC6641733 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature