Catalytic Asymmetric Acyloin Rearrangements of α-Ketols, α-Hydroxy Aldehydes, and α-Iminols by N,N′-Dioxide-Metal Complexes

A highly enantioselective acyloin rearrangement of cyclic alpha-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 ahydroxy aldehydes and alpha-iminols were achieved as well under modified conditions, affording the corresponding chiral alpha-hydroxy ketones and alpha-amino ketones in moderate results. Moreover, further transformations of product to enantioenriched diols were carried out.