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Rhodium-catalyzed enantio- and diastereoselective carboamidation of bicyclic olefins toward construction of remote chiral centers and axis

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Abstract

The precise control of multiple chiral elements through a single step catalytic process remains a significant challenge in asymmetric catalysis. Reported herein is rhodium-catalyzed three-component asymmetric carboamidation between aryl boronic acid, achiral strain-activated symmetric bicyclic olefins bearing a prochiral C–N or N–N axis, and dioxazolones. The reaction proceeded effectively in excellent enantio- and diastereoselectivity under mild conditions to produce the bicyclic framework with six contiguous chiral centers as well as a N–N or C–N chiral axis. The reaction featured excellent functional group tolerance, chemoselectivity, and stereoselectivity. Mechanistic studies indicated that the coupling system proceeded via initial transmetalation, followed by stereo-determining migratory insertion into the olefin and electrophilic amidation.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21525208) and the Fundamental Research Funds for the Central Universities (2020CSLZ005, GK202103031).

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Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, Shaanxi Normal University (SNNU), Xi’an, 710062, China

    Jinlei Wang & Xingwei Li

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  1. Jinlei Wang
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  2. Xingwei Li
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Correspondence to Xingwei Li.

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Supporting information The supporting information is available online at https://chem.scichina.com and https://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

Conflict of interest The authors declare no conflict of interest.

Supporting Information

11426_2023_1646_MOESM1_ESM.pdf

Rhodium-Catalyzed Eantio- and Diastereoselective Carboamidation of Bicyclic Olefins toward Construction of Remote Multiple Chiral Centers and Axis

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Wang, J., Li, X. Rhodium-catalyzed enantio- and diastereoselective carboamidation of bicyclic olefins toward construction of remote chiral centers and axis. Sci. China Chem. 66, 2046–2052 (2023). https://doi.org/10.1007/s11426-023-1646-0

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  • DOI: https://doi.org/10.1007/s11426-023-1646-0

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