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Catalytic Asymmetric Acyloin Rearrangements of α-Ketols, α-Hydroxy Aldehydes, and α-Iminols by <i>N</i>,<i>N</i>′-Dioxide–Metal Complexes

Li Dai, Xiangqiang Li, Zi Zeng, Shunxi Dong, Yuqiao Zhou, Xiaohua Liu, Xiaoming Feng

2020Organic Letters33 citationsDOI

Abstract

A highly enantioselective acyloin rearrangement of cyclic α-ketols has been developed with a chiral Al(III)–N,N′-dioxide complex as catalyst. This strategy provided an array of optically active 2-acyl-2-hydroxy cyclohexanones in moderate to good yields with high enantioselectivities. The asymmetric isomerizations of acyclic α-hydroxy aldehydes and α-iminols were achieved as well under modified conditions, affording the corresponding chiral α-hydroxy ketones and α-amino ketones in moderate results. Moreover, further transformations of product to enantioenriched diols were carried out.

Topics & Concepts

ChemistryCatalysisMetalCombinatorial chemistryOrganic chemistryAsymmetric Synthesis and CatalysisOxidative Organic Chemistry ReactionsAsymmetric Hydrogenation and Catalysis