Li Qian, Fei Jiawei, Ruan Kaidong, Hua Yuhui, Chen Dafa, Luo Ming, Xia Haiping
State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University Xiamen 361005 China.
Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology Shenzhen 518055 China
Chem Sci. 2023 Apr 24;14(21):5672-5680. doi: 10.1039/d3sc01491f. eCollection 2023 May 31.
Reshaping an aromatic framework to generate other skeletons is a challenging issue due to the stabilization energy of aromaticity. Such reconfigurations of aromatics commonly generate non-aromatic products and hardly ever reshape to a different aromatic framework. Herein, we present the transformation of metallaindenols to metallapentalenes and metallaindenes in divergent pathways, converting one aromatic framework to another with an extension of the conjugation framework. The mechanistic study of this transformation shows that phosphorus ligands play different roles in the divergent processes. Further theoretical studies indicate that the expansion of the aromatic system is the driving force promoting this skeletal rearrangement. Our findings offer a new concept and strategy to reshape and construct aromatic compounds.
由于芳香性的稳定能，重塑芳香骨架以生成其他骨架是一个具有挑战性的问题。这种芳烃的重新构型通常会生成非芳香性产物，几乎不会重塑为不同的芳香骨架。在此，我们展示了金属茚醇通过不同途径转化为金属戊搭烯和金属茚，将一个芳香骨架转化为另一个，同时扩展共轭骨架。对该转化的机理研究表明，磷配体在不同过程中发挥不同作用。进一步的理论研究表明，芳香体系的扩展是促进这种骨架重排的驱动力。我们的发现为重塑和构建芳香化合物提供了新的概念和策略。
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