Asymmetric Baylis-Hillman rearrangement

There has been a continuing effort to make the Baylis-Hillman reaction a catalytic asymmetric process. Scott Schnauss of Boston University recently reported (J. Am. Chem. Soc. 125 12094, 2003) an elegant solution to this problem, based on the use of Binol-derived Bronsted acids as catalysts. The product hydroxy enones such as 6 are interesting in themselves, and also as substrates for further transformation, for instance by Claisen rearrangement. 

An asymmetric allylic alkylation of Morita-Baylis-Hillman carbonates and )0-keto sul-fones by modified cinchona alkaloids as catalysts gives products that undergo a Smiles rearrangement-sulfinate addition cascade to functionalized five-membered cyclic sul-fones (Scheme 172) ... 

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