Zhang X,
Shen Y,
Rovis T.
*
Columbia University, New York, USA
Photoinduced Nickel-Catalyzed Selective
N-Demethylation of Trialkylamines Using C(sp
2)–Bromides as HAT Reagents.
J. Am. Chem. Soc. 2023;
145: 3294-3300
Key words
aryl bromides - hydrogen atom transfer - N-demethylation - nickel catalysis - photoinduced catalysis - trialkylamines - vinyl bromides
Significance
Rovis and co-workers report a photoinduced nickel-catalyzed protocol for the N-demethylation of trialkylamines. In contrast to classical approaches, the use of C(sp2)–bromides as hydrogen atom transfer (HAT) reagents allows for selective demethylation over debenzylation.
Comment
Mechanistic studies support the shown mechanism, where photoinduced Ni–C(sp2) bond homolysis leads to the formation of a vinyl (or aryl) radical that is involved in the α-amino radical generation by hydrogen atom abstraction from the trialkylamine.
