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

摘要

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.

关键词