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Updated: Aug 11, 2026

A Protocol for Safe Lithiation Reactions Using Organolithium Reagents
Published on: November 12, 2016
Ylidic radical-molecule reactions
Hong-Bin Xie1, Yi-Hong Ding, Chia-Chung Sun
1State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, People's Republic of China.
Abstract:
The known reactions between a neutral radical and a neutral closed-shell sigma-type molecule are generally associated with the atom/group-abstraction (e.g., CN, OH reactions) or the carbenoid insertion processes (e.g., CH reactions). In this article, we describe a new type of neutral radical-molecule reaction that feature the nucleophilic addition and elimination mechanism based on the systematic Gaussian-3//MP2(full)/6-31G(d) investigations on the PH(3)CH+HX model reactions (X = CH(3), NH(2), OH, F, CH(2)F, CHF(2), CF(3), NHCH(3)/CH(2)NH(2), OCH(3)/CH(2)OH). The novel properties are found to benefit both from the radical and ylidic characters of PH(3)CH, and the type of reagent HX determines the nucleophilic addition reactivity. The present work is the first study on the chemical reactivity of the ylidic radicals.
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