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Catalyst-controlled enantioselective 1,1-arylboration of unactivated olefins

Nature Catalysis volume 3, pages 951–958 (2020)Cite this article

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Abstract

Enantioselective difunctionalization of alkenes constitutes an efficient strategy to assemble complex chiral molecules from simple racemic or achiral starting materials. Here we present an intermolecular nickel-catalysed enantioselective 1,1-arylboration of unactivated terminal alkenes. The high regio- and enantioselectivities of the reactions arise from a judicious choice of the nickel catalyst rather than the incorporation of a directing group. Moreover, excellent regioselectivities can also be obtained from the reactions of allylbenzenes. We also conducted a series of stereospecific downstream transformations for the enantioenriched secondary boronic esters. These examples represent an efficient catalyst-controlled enantioselective 1,1-difunctionalization of unactivated alkenes.

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Fig. 1: Alkene difunctionalizations and synthesis of chiral secondary boron compounds.
Fig. 2: Reactions of gaseous olefins and mechanistic investigations.
Fig. 3

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Data availability

The findings of this study are available within the paper and its Supplementary Information. All data are available from the authors upon reasonable request.

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Acknowledgements

We thank Q. Zhou, W.-B. Liu, A. Lei and X. Zhang at Wuhan University for lending lab space and sharing the basic instruments. We are grateful for the financial support from the National Natural Science Foundation of China (21702151, 21871211) and the Fundamental Research Funds for Central Universities (2042019kf0208). We thank S. Liu for her help with the NMR measurements. We acknowledge W. Reid (RWTH Aachen University) for his insightful discussion and generous help on the manuscript preparation.

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

    Wang Wang, Chao Ding & Guoyin Yin

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W.W. designed and carried out most of the chemical reactions and analysed the data. W.W. and C.D. supported the design and performance of synthetic experiments. G.Y. designed and supervised the project. G.Y. and W.W. wrote the manuscript.

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Correspondence to Guoyin Yin.

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Supplementary Methods, Figs. 1–279, Tables 1–3 and references.

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Wang, W., Ding, C. & Yin, G. Catalyst-controlled enantioselective 1,1-arylboration of unactivated olefins. Nat Catal 3, 951–958 (2020). https://doi.org/10.1038/s41929-020-00523-8

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