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Updated: Nov 7, 2025

Continuous Flow Chemistry: Reaction of Diphenyldiazomethane with p-Nitrobenzoic Acid
Published on: November 15, 2017
Mechanistic insights into the dearomative diborylation of pyrazines: a radical or non-radical process?
Liuzhou Gao1, Hanyin Zhang1, Xueting Liu1
1Key Laboratory of Mesoscopic Chemistry of Ministry of Education, Institute of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, P. R. China. shuhua@nju.edu.cn wangguoqiang710@nju.edu.cn.
Abstract:
The mechanisms of the dearomative diborylation of pyrazines were investigated via a combination of density functional theory (DFT) calculations and experimental studies. DFT calculations revealed that a non-radical mechanism involving two successive [3,3]-σ-rearrangement-type processes is responsible for the diborylation of pyrazine with bis(pinacolato)diboron (B2pin2). However, this non-radical process is highly unfavorable for the diborylation reaction of sterically hindered pyrazine (2,3-dimethylpyrazine). For the diboration reaction of 2,3-dimethylpyrazine with B2pin2 in the presence of 2,6-dichloro-4,4'-bipyridine as the catalyst, 4,4'-bipyridine-mediated radical pathway proceeding through a B-B homolytic cleavage/boryl radical addition is preferred. Control experiments combined with kinetic studies provided supportive evidence for the proposed mechanism.
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