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Synfacts 2023; 19(05): 0461
DOI: 10.1055/s-0042-1752435
Metals in Synthesis

Cutting Me Off: Selective N-Demethylation of Trialkylamines Using C(sp2)–Bromides as HAT Reagents

Contributor(s):
Martin Oestreich
,
Hendrik F. T. Klare
,
Daniel Brösamlen
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
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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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