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DOI: 10.1055/a-2657-1791
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Ring-Opening Metathesis of Benzene Induced by Rare-Earth Metallacycles

College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare-earth Materials Chemistry and Applications & Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Peking University, Beijing, China
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Wen-Xiong Zhang
College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory of Rare-earth Materials Chemistry and Applications & Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, Peking University, Beijing, China
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This work was supported by the National Key R&D Program of China (no. 2021YFF0701600), National Natural Science Foundation of China (nos. 22371006, 22131001, 21725201, 21890721) and Beijing National Laboratory for Molecular Sciences (BNLMS-CXXM-202401).
Supported by: National Natural Science Foundation of China 21725201,21890721,22131001,22371006
Supported by: Beijing National Laboratory for Molecular Sciences BNLMS-CXXM-202401


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Abstract

Activation of inert C–C bonds in arenes remains a formidable challenge in synthetic chemistry. Despite advances in arene C–C bond activation, metathesis transformations of aromatic C–C bonds remain largely unexplored. Recently, we uncovered a rare-earth metal-enabled intramolecular metathesis between a benzene C–C bond and a C–C single bond, assisted by the high reactivity and synergistic effect of rare-earth metallacycles. Mechanistic studies reveal a stepwise [2+2] cycloaddition/cycloreversion sequence via a fused tricyclic intermediate. This transformation expands the chemical space of arene reactivity, providing a rare example of aromatic ring-opening metathesis through a noncarbene pathway.



Publication History

Received: 04 June 2025

Accepted after revision: 14 July 2025

Article published online:
01 August 2025

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