Photoredox catalysis has become an indispensable solution for the synthesis of small organic molecules.However,the precise construction of single-atomic active sites not only determines the catalytic performance,but a...Photoredox catalysis has become an indispensable solution for the synthesis of small organic molecules.However,the precise construction of single-atomic active sites not only determines the catalytic performance,but also avails the understanding of structure–activity relationship.Herein,we develop a facile approach to immobilize single-atom Ni sites anchored porous covalent organic framework(COF)by use of 4,4',4''-(1,3,5-triazine-2,4,6-triyl)trianiline and 2,6-diformylpyridine(Ni SAS/TD-COF).Ni SAS/TDCOF catalyst achieves excellent catalytic performance in visible-light-driven catalytic carbon–nitrogen cross-coupling reaction between aryl bromides and amines under mild conditions.The reaction provides amine products in excellent yields(71%–97%)with a wide range of substrates,including aryl and heteroaryl bromides with electron-deficient,electron-rich and neutral groups.Notably,Ni SAS/TD-COF could be recovered from the reaction mixture,corresponding to the negligible loss of photoredox performance after several cycles.This work provides a promising opportunity upon rational design of single-atomic active sites on COFs and the fundamental insight of photoredox mechanism for sustainable organic transformation.展开更多
基金supported by the National Natural Science Foundation of China(21972015 and 22088102)Young top talents project of Liaoning Province(XLYC1907147)+1 种基金the Liaoning Revitalization Talent Program(XLYC2008032)the Fundamental Research Funds for the Central Universities(DUT22LAB602)。
文摘Photoredox catalysis has become an indispensable solution for the synthesis of small organic molecules.However,the precise construction of single-atomic active sites not only determines the catalytic performance,but also avails the understanding of structure–activity relationship.Herein,we develop a facile approach to immobilize single-atom Ni sites anchored porous covalent organic framework(COF)by use of 4,4',4''-(1,3,5-triazine-2,4,6-triyl)trianiline and 2,6-diformylpyridine(Ni SAS/TD-COF).Ni SAS/TDCOF catalyst achieves excellent catalytic performance in visible-light-driven catalytic carbon–nitrogen cross-coupling reaction between aryl bromides and amines under mild conditions.The reaction provides amine products in excellent yields(71%–97%)with a wide range of substrates,including aryl and heteroaryl bromides with electron-deficient,electron-rich and neutral groups.Notably,Ni SAS/TD-COF could be recovered from the reaction mixture,corresponding to the negligible loss of photoredox performance after several cycles.This work provides a promising opportunity upon rational design of single-atomic active sites on COFs and the fundamental insight of photoredox mechanism for sustainable organic transformation.
