北京大学张文雄团队报道了稀土金属实现苯开环复分解。相关研究成果于2024年12月12日发表于国际顶尖学术期刊《美国化学会杂志》。

芳烃中惰性C-C键的活化和转化是合成化学中具有挑战性和重要意义的课题。虽然有一些关于芳烃环中C-C键活化的报道，但涉及芳烃C-C键的复分解反应领域仍未得到探索。

该文中，研究人员报告了一种稀土金属使一个苯C-C键和另一个C-C单键的分子内复分解反应，该反应得到了稀土金属环的高反应性和独特的协同效应的辅助。

机理研究揭示了一条有趣的途径，即通过逐步[2+2]环加成反应，然后逐步[2+2]环回复反应，形成带有4元环的稠合三环中间体。发现的独特反应扩展了芳烃的反应性，有望激发芳香开环复分解反应的发展。

附：英文原文

Title: Rare-Earth Metal-Enabled Ring-Opening Metathesis of Benzene

Author: Wei Liu, Ping Wu, Yibo Liang, Junnian Wei, Gen Luo, Wen-Xiong Zhang

Issue&Volume: December 12, 2024

Abstract: Activation and transformation of inert C–C bonds within arenes are challenging and important topics in synthetic chemistry. While there have been some reports on the activation of C–C bonds in arene rings, the realm of metathesis reactions involving arene C–C bonds remains unexplored. Here, we report a rare-earth metal-enabled intramolecular metathesis reaction of one benzene C–C bond and another C–C single bond, assisted by the high reactivity and unique synergistic effect of rare-earth metallacycles. Mechanistic studies disclose an intriguing pathway that forms a fused tricyclic intermediate bearing a 4-membered ring through stepwise [2 + 2] cycloaddition, followed by stepwise [2 + 2] cycloreversion. The distinct reaction discovered here extends the reactivity of arenes and is expected to inspire the development of aromatic ring-opening metathesis reactions.

DOI: 10.1021/jacs.4c15650

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c15650