title: Visible-Light Photoredox-Catalyzed C-H Difluoroalkylation of Hydrazones through an Aminyl Radical/Polar Mechanism.
abstract: An unprecedented visible-light-induced direct C-H bond difluoroalkylation of aldehyde-derived hydrazones was developed. This reaction represents a new way to synthesize substituted hydrazones. The salient features of this reaction include difluorinated hydrazone synthesis rather than classical amine synthesis, extremely mild reaction conditions, high efficiency, wide substrate scope, ease in further transformations of the products, and one-pot syntheses. Mechanistic analyses and theoretical calculations indicate that this reaction is enabled by a novel aminyl radical/polar crossover mechanism, with the aminyl radical being oxidized into the corresponding aminyl cation through a single electron transfer (SET) process.
authors.affiliation: State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, P. R. China.
authors.forename: Pan
authors.initials: P
authors.lastname: Xu
authors.affiliation: Key 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.
authors.forename: Guoqiang
authors.initials: G
authors.lastname: Wang
authors.affiliation: State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, P. R. China.
authors.forename: Yuchen
authors.initials: Y
authors.lastname: Zhu
authors.affiliation: State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, P. R. China.
authors.forename: Weipeng
authors.initials: W
authors.lastname: Li
authors.affiliation: State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, P. R. China.
authors.forename: Yixiang
authors.initials: Y
authors.lastname: Cheng
authors.affiliation: Key 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.
authors.forename: Shuhua
authors.initials: S
authors.lastname: Li
authors.affiliation: State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, P. R. China. cjzhu@nju.edu.cn.|State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Shanghai, 200032, P. R. China. cjzhu@nju.edu.cn.
authors.forename: Chengjian
authors.initials: C
authors.lastname: Zhu
keywords: fluorine; hydrazones; imines; photocatalysis; radical reactions