Catalytic enantioselective synthesis of β-amino alcohols by nitrene insertion  

作　　者：Zijun Zhou Yuqi Tan Xiang Shen Sergei Ivlev Eric Meggers 

机构地区：[1]Fachbereich Chemie,Philipps-Universitat Marburg,Hans-Meerwein-Strasse 4,35043 Marburg,Germany

出　　处：《Science China Chemistry》2021年第3期452-458,共7页中国科学（化学英文版）

基　　金：supported by the Deutsche Forschungsgemeinschaft(ME 1805/15-1)。

摘　　要：Chiral β-amino alcohols are important building blocks for the synthesis of drugs, natural products, chiral auxiliaries, chiral ligands and chiral organocatalysts. The catalytic asymmetric β-amination of alcohols offers a direct strategy to access this class of molecules. Herein, we report a general intramolecular C(sp^(3))–H nitrene insertion method for the synthesis of chiral oxazolidin-2-ones as precursors of chiral β-amino alcohols. Specifically, the ring-closing C(sp^(3))–H amination of N-benzoyloxycarbamates with 2 mol% of a chiral ruthenium catalyst provides cyclic carbamates in up to 99% yield and with up to 99% ee.The method is applicable to benzylic, allylic, and propargylic C–H bonds and can even be applied to completely non-activated C(sp^(3))–H bonds, although with somewhat reduced yields and stereoselectivities. The obtained cyclic carbamates can subsequently be hydrolyzed to obtain chiral β-amino alcohols. The method is very practical as the catalyst can be easily synthesized on a gram scale and can be recycled after the reaction for further use. The synthetic value of the new method is demonstrated with the asymmetric synthesis of a chiral oxazolidin-2-one as intermediate for the synthesis of the natural product aurantioclavine and chiral β-amino alcohols that are intermediates for the synthesis of chiral amino acids, indane-derived chiral Box-ligands, and the natural products dihydrohamacanthin A and dragmacidin A.

关 键 词：asymmetric catalysis NITRENE AMINATION chiral-at-metal RUTHENIUM 

分 类 号：O623.734[理学—有机化学]