Pummerer反応について--反応機構を中心にして
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概要
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The mechanisms of various Pummerer type reactions of sulfoxides and other trivalent sulfur compounds, such as sulfilimines and sulfonium ylides, are critically analyzed and discussed based on numerous observations on both stereochemistry and kinetic experiments together with <SUP>18</SUP>O and D tracer experiments. Several stereospecific reactions are described. Particularly interesting is an asymmetric induction to α-carbon in the reaction of optically active sulfoxides with acetic anhydride which is considered to proceed through an exclusively intramolecular acetoxy migration via an intimate ion-pair derived by S-O bond cleavage of the incipient acetoxysulfonium ylide formed in the early stage of the reaction. Several examples of intramolecular Pummerer reactions and many other Pummerer reactions which proceed via an ion-pair process are also given. Finally, the Pummerer reaction for a model pathway for enzymatic oxidative demethylation of methionine is briefly described.
- 社団法人 有機合成化学協会の論文