シリルケテンアセタールを用いる不斉Pummerer型反応

概要

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The asymmetric Pummerer reaction of optically active sulfoxides is of significant interest because it would provide a way to synthesize chiral, non- racemic α-substituted sulfides, and has attracted considerable attention from both synthetic and mechanistic points of view. The yields of enantiomeric excess, however, were quite low for acyclic sulfoxides. We found a novel silicon-induced Pummerer-type rearrangement, an additive Pummerer- type reaction and an intramolecular Pummerer- type cyclization of sulfoxides using O-methyl-O-tert-butyldimethylsilyl ketene acetal under mild conditions and applied this method to the first highly asymmetric transfer reaction of chiral, non-racemic acyclic sulfoxides. In this review, we mainly describe the asymmetric Pummerer-type rearrangement, the asymmetric Pummerer-type cyclization of chiral, non-racemic sulfoxides and its application to the biomimetic conversion of Arnstein tripeptide analogues into optically active cis-β-lactams related to Penicillin biosynthesis.
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