Photoredox Catalysis Unlocks the Nickel-Catalyzed Cyanation of Aryl Halides under Benign Conditions  

作　　者：Yue Jia Yi-Yin Liu Liang-Qiu Lu Shi-Han Liu Hong-Bin Zhou Yu Lan Wen-Jing Xiao 

机构地区：[1]CCNU-uOttawa Joint Research Centre,Key Laboratory of Pesticide&Chemical Biology,Ministry of Education,College of Chemistry,Central China Normal University,Wuhan 430079 [2]School of Chemistry and Chemical Engineering,Chongqing University,Chongqing 400030 [3]Province College of Chemistry,Institute of Green Catalysis,Zhengzhou University,Zhengzhou 450001 [4]State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032

出　　处：《CCS Chemistry》2022年第5期1577-1586,共10页中国化学会会刊（英文）

基　　金：the National Science Foundation of China(nos.21822103,21820102003,21822303,21772052,21772053,and 91956201);the Program of Introducing Talents of Discipline to Universities of China(111 Program,B17019);the Natural Science Foundation of Hubei Province(no.2017AHB047).

摘　　要：The transition-metal-catalyzed cyanations of aryl halides are among the most used methods for synthesizing aryl nitriles.Despite tremendous advances,cyanating an aryl halide in a facile and benign fashion has generally been unsuccessful.The challenge in this significant transformation is the strong affinity of cyanide for metals,which hampers oxidative addition(OD)and reductive elimination(RE)making organometallic catalysis elusive.Herein,we demonstrate for the first time that photoredox-nickel-catalyzed cyanations of aryl halides are readily enabled by visible light,in which Ni(Ⅱ)species are transiently oxidized to Ni(Ⅲ)species,thereby facilitating subsequent cyanide transfer and RE.Using this dual catalysis strategy,we cyanated aryl and alkenyl halides at room temperature in a highly benign manner(30 examples,53-93% yield)by avoiding the use of air-sensitive ligands,Ni(0)precursors,and hypertoxic cyanation reagents,while also limiting excess metal waste.Computational studies were also used to help understand the present transformation.

关 键 词：nickel catalysis photoredox catalysis visible light cyanation reaction aryl nitrile 

分 类 号：O62[理学—有机化学]