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Published on: November 9, 2019
Cobalt-catalyzed enantioselective desymmetrizing reductive cyclization of alkynyl cyclodiketones
Ren-Xiao Liang1, Heng-Wei Tang1, Jia-Liang Liu1
1College of Chemical Engineering, State Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, Zhejiang University of Technology Chaowang Road 18# Hangzhou 310014 China liangrx@zjut.edu.cn yxjia@zjut.edu.cn.
Abstract:
A highly enantioselective cobalt-catalyzed desymmetrizing reductive cyclization of alkynyl cyclodiketones has been developed. Under mild reaction conditions by employing HBpin as a reducing agent and ferrocene-based PHOX as a chiral ligand, a series of polycyclic tertiary allylic alcohols bearing contiguous quaternary stereocenters are achieved in moderate to excellent yields with excellent enantioselectivities (up to 99%). Broad substrate scope and high functional group compatibility are observed in this reaction. A CoH-catalyzed pathway involving alkyne hydrocobaltation followed by nucleophilic addition to the C[double bond, length as m-dash]O bond is proposed. Synthetic transformations of the product are conducted to demonstrate the practical utilities of this reaction.
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