Affiliation:
1. College of Chemistry Green Catalysis Center International Phosphorus Laboratory Zhengzhou University 450001 Zhengzhou China
Abstract
AbstractHerein, 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.
Funder
National Natural Science Foundation of China
Subject
General Chemistry,Catalysis,Organic Chemistry