Organophotocatalytic Generation of N- and O-Centred Radicals Enables Aerobic Oxyamination and Dioxygenation of Alkenes.
A cooperative TEMPO and photoredox catalytic strategy was applied for the first time to the direct conversion of N-H and O-H bonds into N- and O-centred radicals, enabling a general and selective oxidative radical oxyamination and dioxygenation of various β,γ-unsaturated hydrazones and oximes. In the reaction, O2 was employed not only as a terminal oxidant but also as the oxygen source. This protocol provided efficient access to the synthesis of various synthetically and biologically important pyrazoline, pyridazine and isoxazoline derivatives under metal-free and mild reaction conditions. Mechanistic studies revealed that the cooperative organophotocatalytic system functions through two single-electron-transfer (SET) processes.
CCNU-uOttawa Joint Research Center, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University (CCNU), 152 Luoyu Road, Wuhan, Hubei, 430079, P. R. China.
Xiao-Qiang
XQ
Hu
CCNU-uOttawa Joint Research Center, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University (CCNU), 152 Luoyu Road, Wuhan, Hubei, 430079, P. R. China.
Jun
J
Chen
CCNU-uOttawa Joint Research Center, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University (CCNU), 152 Luoyu Road, Wuhan, Hubei, 430079, P. R. China. chenjiarong@mail.ccnu.edu.cn.
Jia-Rong
JR
Chen
CCNU-uOttawa Joint Research Center, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University (CCNU), 152 Luoyu Road, Wuhan, Hubei, 430079, P. R. China.
Dong-Mei
DM
Yan
CCNU-uOttawa Joint Research Center, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University (CCNU), 152 Luoyu Road, Wuhan, Hubei, 430079, P. R. China.|Collaborative Innovation Center of Chemical Science and Engineering, Tianjin, 300072, P. R. China.
Wen-Jing
http://orcid.org/0000-0002-9318-6021
WJ
Xiao
hydrazones; nitrogen radicals; oximes; oxygen radicals; photocatalysis