Explorations into the Potential of Chiral Sulfonium Reagents to Effect Asymmetric Halonium Additions to Isolated Alkenes

Dedicated to Prof. Scott E. Denmark on the occasion of his 60^th birthday

Abstract

While methods for the racemic dihalogenation and halohydroxylation of alkenes have been known for decades, enantioselective variants of these processes remain elusive. Initial attempts were made to overcome this long-standing challenge by exploring the potential of chiral, crystalline, sulfur-derived halonium reagents to accomplish the asymmetric dichlorination and iodohydroxylation of 1,2-dihydronaphthalene. Asymmetric dichlorination of this substrate was achieved in 57% yield and 14% enantiomeric excess (ee), but asymmetric iodohydroxylation was much more successful, giving 67% yield and 63% ee. Thorough studies were made of these processes, including investigation of various chiral sulfide derivatives, their substrate scopes, and the reaction conditions.

Key words

chirality - halogenations - alkenes - enantioselectivity - hydroxylations

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