合成化学2024,Vol.32Issue(5) :414-423.DOI:10.15952/j.cnki.cjsc.1005-1511.23071

可见光氧化还原协同镍催化构建C—S键偶联反应

Visible Redox Synergizes with Nickel Catalyst to Construct C—S Bond Reaction

李申 剧芳 张舒雅 丁晶晶 康舒铭
合成化学2024,Vol.32Issue(5) :414-423.DOI:10.15952/j.cnki.cjsc.1005-1511.23071

可见光氧化还原协同镍催化构建C—S键偶联反应

Visible Redox Synergizes with Nickel Catalyst to Construct C—S Bond Reaction

李申 1剧芳 1张舒雅 1丁晶晶 1康舒铭1
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作者信息

  • 1. 合肥工业大学化学化工学院,安徽省先进催化材料与反应工程重点实验室,安徽合肥 230009
  • 折叠

摘要

在可见光和过渡金属镍协同催化体系中,可见光催化可以通过单电子氧化或还原过程推动过渡金属镍催化,又可以通过能量转移过程推动镍催化循环.这为传统过渡金属催化的偶联反应提供了更多可能性.同时,大多数光催化剂使用基于Ru和Ir金属的配合物,不仅价格昂贵,还会在工业生产中存在金属残留.本文开发了一种高效且经济的协同催化体剂(Nap)2PXZ-bpy-Ni,以吩噁嗪为有机光催化剂,NiBr2·DME为镍催化剂,联吡啶作为配体,通过Click的方式将光催化剂和联吡啶镍催化剂连接起来.实验结果表明:在1%(物质的量分数,下同)催化剂负载下反应12H,C—S键偶联产物收率可达73%~95%,实现了高效的催化效率并显示出较好的官能团适用性和底物普适性.最后通过自由基捕捉实验推测了该反应可能的机理.

Abstract

In the synergistic catalytic system of visible light and transition metal nickel,visible photo-catalysis can promote transition metal nickel catalysis through single-electron oxidation or reduction process,and can promote nickel catalytic cycle through energy transfer process.This opens up more possibilities for coupling reactions catalyzed by traditional transition metals.At the same time,most photocatalysts use complexes based on Ru and Ir metals,which are not only expensive,but also have metal residue problems in industrial production.In this paper,a highly efficient and economical syner-gistic catalyst(Nap)2 PXZ-bpy-Ni was developed,with phenoxazine as the organic photocatalyst,NiBr2·DME as the nickel catalyst,and bipyridine as the ligand,which connects the photocatalyst and the bipyridine nickel catalyst by Click.The experimental results show that the yield of C—S bond cou-pling products can reach 73%~95%under 1%catalyst loading for 12 h,achieving efficient catalytic efficiency and showing good functional group applicability and substrate universality.Finally,the pos-sible mechanism of the reaction was speculated by free radical capture experiments.

关键词

光催化/镍催化/协同催化/有机光敏剂/C—S偶联反应

Key words

photoredox catalysis/nickel catalysis/synergistic catalysis/organic photosensitizer/C—S coupling reaction

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基金项目

国家自然科学基金(21771049)

出版年

2024
合成化学
四川省化学化工学会 中国科学院成都有机化学研究所

合成化学

CSTPCD
影响因子:0.42
ISSN:1005-1511
参考文献量19
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