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Aromatic and olefinic C-H alkenylation by catalysis with spirocyclic NHC Ru(IV) pincer complex

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Abstract

Catalyst innovation lies at the heart of transition-metal-catalyzed reaction development. In this article, we have explored the C(sp2)—H alkenylation activity with novel spirocyclic N-heterocyclic carbene (NHC)-based cyclometalated ruthenium pincer catalyst system, SNRu-X. After screening catalyst and condition, a high valent Ru(IV) dioxide (X = O2) species has demonstrated superior reactivity in the catalytic alkenylation of aromatic and olefinic C-H bonds with unactivated alkenyl bromides and triflates. This reaction has achieved the easy construction of a wide range of (hetero)aromatic alkenes and dienes, in good to excellent yields with exclusive selectivity. Preliminary mechanistic studies indicate that this reaction may proceed through a single electron transfer (SET) triggered oxidative addition, by doing so, providing valuable complementary to classical alke-nylation reactions that are dependent on activated alkenyl precursors.

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Acknowledgements

This work was suported by the National Natural Science Foundation of China (2187,1117, 91956203), the “111” Program of Minister of Education, Beijing National Laboratory for Molecular Sciences (BNLMS202109) and the Science and Technology Commission of Shanghai Municipality (19JC1430100). We also thank Prof. Lu Zhan (Zhejiang University) for his kind assistant HRMS analysis.

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Authors and Affiliations

  1. State Key Laboratory of Applied Organic Chemistry & College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000, China

    Heng Cai, Yong-Qiang Tu, Ka Lu, Qi-Long Chen, Fu-Min Zhang, Xiao-Ming Zhang & Zhi-Bo Yan

  2. School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai, 200240, China

    Yong-Qiang Tu

  3. Department of Chemistry, Zhejiang University, Hangzhou, 310027, China

    Yuan-Jiang Pan

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  1. Heng Cai
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Correspondence to Yong-Qiang Tu.

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Supporting information The supporting information is available online at http://chem.scichina.com and http://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.

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Cai, H., Tu, YQ., Lu, K. et al. Aromatic and olefinic C-H alkenylation by catalysis with spirocyclic NHC Ru(IV) pincer complex. Sci. China Chem. 66, 2791–2796 (2023). https://doi.org/10.1007/s11426-022-1541-5

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