1. π‐Electron Fluctuation‐Induced P+/C− Ambiphilic Interaction for Intramolecular CAr−H Bond Activation.
- Author
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Chen, Jianzhou, Wang, Junjian, Wang, Xinghua, Wei, Donghui, and Duan, Zheng
- Subjects
RESONANCE ,PHOSPHORUS ,ATOMS ,CARBON - Abstract
Herein, we describe how computational mechanistic understanding has led directly to the discovery of new 2H‐phosphindole for C−CAr bond activation and dearomatization reaction. We uncover an unexpected intramolecular C−H bond activation with a 2H‐phosphindole derivative. This new intriguing experimental observation and further theoretical studies led to an extension of the reaction mechanism with 2H‐phosphindole. Through DFT calculations, we confirm that within a five‐membered ring, the polarizable PC3 unit orchestrates the formation of an electrophilic phosphorus atom (P+) and a nucleophilic carbon atom (C−). This kinetically accessible ambiphilic phosphorus/carbon couple is spatially separated by geometric constraints, and their reactivity is modulated through structural resonance. [ABSTRACT FROM AUTHOR]
- Published
- 2024
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