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Synfacts 2023; 19(05): 0461
DOI: 10.1055/s-0042-1752435
DOI: 10.1055/s-0042-1752435
Metals in Synthesis
Cutting Me Off: Selective N-Demethylation of Trialkylamines Using C(sp2)–Bromides as HAT Reagents
Zhang X,
Shen Y,
Rovis T.
*
Columbia University, New York, USA
Photoinduced Nickel-Catalyzed Selective N-Demethylation of Trialkylamines Using C(sp2)–Bromides as HAT Reagents.
J. Am. Chem. Soc. 2023;
145: 3294-3300
DOI: 10.1021/jacs.2c12767
Photoinduced Nickel-Catalyzed Selective N-Demethylation of Trialkylamines Using C(sp2)–Bromides as HAT Reagents.
J. Am. Chem. Soc. 2023;
145: 3294-3300
DOI: 10.1021/jacs.2c12767
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.
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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.
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Publication History
Article published online:
14 April 2023
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