Nickel Photocatalyzed Reductive 1,4-Dicarbofunctionalization of 1,3-Enynes with N-Methylamines and Organohalides Enabled by Site-Selective C(sp3)-H Functionalization

作者：Cheng, Chaozhihui; Lv, Gui-Fen; Wu, Shuang^*; Li, Yang; Li, Jin-Heng^*

来源：Organic Letters, 2023, 25(23): 4236-4240.

DOI：10.1021/acs.orglett.3c01103

• ALPHA-IMINO ESTERS
• CYCLIZATION REACTIONS
• ASYMMETRIC-SYNTHESIS
• AMINO-ACIDS
• ALLENES

A cooperative nickel and photoredox reductive catalysisfor 1,4-dicarbofunctionalizationof 1,3-enynes with tertiary N-methylamines and organohalidesto produce tetrasubstituted allenes is presented. This method enablesthe generation of the aminoalkyl C(sp(3))-centered radicalsby site selective cleavage of the N-methyl C(sp(3))-H bonds in tertiary N-methylaminesand is extended to alkyl bromides as the electrophilic terminatingregents. Mechanistic studies indicate that the reaction involves aradical process and a Ni-0/Ni-I/Ni-III catalytic cycle.

• 单位
  兰州大学; 南昌航空大学