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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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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DOI: https://doi.org/10.1007/s11426-022-1541-5