Wong Kong Ching, Ng Elvis, Wong Wing-Tak, Chiu Pauline
State Key Laboratory of Synthetic Chemistry, Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China.
Department of Pharmacology and Pharmacy, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China.
Chemistry. 2016 Mar 7;22(11):3709-12. doi: 10.1002/chem.201504870. Epub 2016 Feb 4.
An efficient reductive Claisen rearrangement, catalyzed by in situ generated copper hydride and stoichiometric in diethoxymethylsilane, has been developed. Yields of up to 95 % with good to excellent diastereoselectivities were observed in this reaction. Mechanistic studies showed that the stereospecific rearrangement proceeded via a chair transition state of (E)-silyl ketene acetals as intermediates and not via the copper enolates.
已开发出一种高效的还原克莱森重排反应，该反应由原位生成的氢化铜催化，且二乙氧基甲基硅烷为化学计量反应物。在该反应中观察到产率高达95%，非对映选择性良好至优异。机理研究表明，立体专一性重排通过（E）-硅基烯酮缩醛的椅式过渡态作为中间体进行，而非通过铜烯醇盐。
