Volume 62, Issue 35 e202308041
Research Article

Base-Modulated 1,3-Regio- and Stereoselective Carboboration of Cyclohexenes

Weiyu Kong

Weiyu Kong

The Institute for Advanced Studies, Wuhan University, Wuhan, Hubei, 430072 P. R. China

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Yang Bao

Yang Bao

The Institute for Advanced Studies, Wuhan University, Wuhan, Hubei, 430072 P. R. China

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Liguo Lu

Liguo Lu

The Institute for Advanced Studies, Wuhan University, Wuhan, Hubei, 430072 P. R. China

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Zhipeng Han

Zhipeng Han

The Institute for Advanced Studies, Wuhan University, Wuhan, Hubei, 430072 P. R. China

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Yifan Zhong

Yifan Zhong

The Institute for Advanced Studies, Wuhan University, Wuhan, Hubei, 430072 P. R. China

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Dr. Ran Zhang

Dr. Ran Zhang

Core Facility of Wuhan University, Wuhan, Hubei, 430072 P. R. China

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Dr. Yuqiang Li

Corresponding Author

Dr. Yuqiang Li

Shanghai AI Laboratory, Shanghai, 200030 P. R. China

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Prof. Dr. Guoyin Yin

Corresponding Author

Prof. Dr. Guoyin Yin

The Institute for Advanced Studies, Wuhan University, Wuhan, Hubei, 430072 P. R. China

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Dedicated to the 130th anniversary of Wuhan University
First published: 10 July 2023
Citations: 3

Graphical Abstract

Introducing two remote functional groups into rings via chain-walking represents a new strategy to efficiently access multi-substituted saturated cyclic compounds. We report an unprecedented 1,3-cis-carboboration of cyclohexenes by nickel catalysis. The application of LiOMe as base plays a crucial role in the success of this reaction.

Abstract

While chain-walking stimulates wide interest in both polymerization and organic synthesis, site- and stereoselective control of chain-walking on rings is still a challenging task in the realm of organometallic catalysis. Inspired by a controllable chain-walking on cyclohexane rings in olefin polymerization, we have developed a set of chain-walking carboborations of cyclohexenes based on nickel catalysis. Different from the 1,4-trans-selectivity disclosed in polymer science, a high level of 1,3-regio- and cis-stereoselectivity is obtained in our reactions. Mechanistically, we discovery that the base affects the reduction ability of B2pin2 and different bases lead to different catalytic cycles and different regioselective products (1,2- Vs 1,3-addition). This study provides a concise and modular method for the synthesis of 1,3-disubstituted cyclohexylboron compounds. The incorporation of a readily modifiable boronate group greatly enhances the value of this method, the synthetic potential of which was highlighted by the synthesis of a series of high-valued commercial chemicals and pharmaceutically interesting molecules.

Conflict of interest

The authors declare no conflict of interest.

Data Availability Statement

The data that support the findings of this study are available in the supplementary material of this article.

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