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Synergistic asymmetric diarylation of tethered alkenes via C–H functionalization of simple (hetero)arenes

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Abstract

By virtue of the atom- and step-economy, utilization of simple arenes as a supplant of pre-prepared aryl metal species or aryl halides for the synthesis of arylated chiral molecules has attracted great attention from the synthetic community. While transition-metal-catalyzed enantioselective diarylation of tethered alkenes has been employed to prepare important chiral cyclic compounds, the direct use of simple arenes as aryl precursors is still underdeveloped, probably due to the difficulties in the effective control of the reactivity, site-selectivity and/or enantioselectivity. Herein we report an asymmetric Pd/Ag dual metal catalytic system for the non-directed, site- and enantioselective domino Heck/intermolecular C–H functionalization of arenes. Mechanistic studies showed that Pd and Ag act in cooperation in the catalysis and the chiral bisphosphine ligand plays a bifunctional role, i.e., assisting the silver species in the cleavage of the aryl C–H bond, while inducing the enantioselectivity on direct complexation with palladium. This method provides an efficient approach to the corresponding chiral oxindoles with good enantiomeric excesses from a broad scope of arenes, including fluoroarenes, heteroarenes and several complex products derived from medicines or natural products.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2021YFA1500100), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB0610000), the National Natural Science Foundation of China (92256303, 22171278, 21821002), the Shanghai Science and Technology Committee (23ZR1482400) and the Natural Science Foundation of Ningbo (2023J034).

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Authors and Affiliations

  1. Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China

    Jian Yao & **aohong Huo

  2. State Key Laboratory of Organometallic Chemistry and Shanghai Hongkong Joint Laboratory in Chemical Synthesis, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, China

    Jian Yao, Can Zhao, Lili Shao & **aoming Wang

  3. School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou, 310024, China

    **aoming Wang

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  1. Jian Yao
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  2. Can Zhao
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  4. **aohong Huo
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  5. **aoming Wang
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Correspondence to **aoming Wang.

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Supporting information The supporting information is available online at chem.scichina.com and springer.longhoe.net/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.

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11426_2024_2059_MOESM1_ESM.pdf

Silver and Palladium Synergistic Asymmetric Diarylation of Tethered Alkenes via C-H Functionalization of Simple (Hetero)Arenes

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Yao, J., Zhao, C., Shao, L. et al. Synergistic asymmetric diarylation of tethered alkenes via C–H functionalization of simple (hetero)arenes. Sci. China Chem. (2024). https://doi.org/10.1007/s11426-024-2059-y

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