摘要
研究了镍/可见光协同催化的溴代芳烃/杂芳烃与醇的C—O键偶联反应.在456 nm蓝光的照射下,以有机光敏剂2,4,5,6-四(9-咔唑基)间苯二腈(4CzIPN)或者2,4,5,6-四(二苯胺基)间苯二腈(4DPAIPN)为光催化剂,以乙二醇二甲醚溴化镍(NiBr2•DME)、配体和碱为协同催化体系,高效地实现了烷基芳基醚类化合物的合成.该反应的可能历程为:Ni(0)中间体先与溴代芳烃发生氧化加成,再与醇进行配体交换;生成的Ni(II)中间体被激发态光催化剂氧化为Ni(III)中间体,继而发生还原消除反应.该反应具有良好的底物适用性,可以用于苄醇、一级醇与二级醇的转化,且官能团兼容性较好.
A nickel/visible light dual-catalyzed C—O bond coupling reaction between aryl/heteroaryl bromides and alcohols has been developed.Alkyl aryl ethers were efficiently synthesized by using organic photoredox-catalyst 2,4,5,6-tetra(9Hcarbazol-9-yl)isophthalonitrile(4CzIPN)or 2,4,5,6-tetrakis(diphenylamino)isophthalonitrile(4DPAIPN)in the presence of nickel(II)bromide 1,2-dimethoxyethane(NiBr2•DME),a ligand,and a base under 456 nm blue LED irradiation at room temperature.The reaction likely involves the oxidative addition of Ni(0)intermediate to aryl bromide,ligand exchange with the alcohol,oxidization of the resulting Ni(II)intermediate by the excited photoredox catalyst to form Ni(III)intermediate,and subsequent reductive elimination.This method exhibits broad substrate scope of alcohols,including benzyl alcohols,primary alcohols,and secondary alcohols,and with remarkable functional group tolerance.
作者
高山
解鑫
刘元红
Gao Shan;Xie Xin;Liu Yuanhong(Henan Institute of Advanced Technology,Zhengzhou University,Zhengzhou 450001;State Key Laboratory of Organometallic Chemistry,Shanghai Inistitute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032;University of Chinese Academy of Sciences,Beijing 100049)
出处
《有机化学》
北大核心
2026年第1期266-278,共13页
Chinese Journal of Organic Chemistry
基金
中国科学院战略性先导科技专项(No.XDB0610000)
河南省科学院高层次人才科研启动基金(No.242002063)资助项目.
关键词
镍催化
可见光
C—O键偶联
烷基芳基醚
nickel-catalysis
visible light
C—O bond coupling
alkyl aryl ethers
