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Synfacts 2025; 21(03): 254
DOI: 10.1055/a-2518-3301
Metals in Synthesis

Copper-Catalyzed Enantioselective Acyloxylation of Activated C(sp3)−H Bonds with Carboxylic Acids

Contributor(s):
Martin Oestreich 
,
Hendrik F. T. Klare 
,
Daniel Brösamlen 
Liu X-M, Li F, Wang T, Dai L, Yang Y, Jiang N-Q, Xue L-Y, Liu J-Y, Xue X-S *, Xiao L-J *, Zhou Q-L *. Shanghai Institute of Organic Chemistry and Nankai University, Tianjin, P. R. China
Catalytic Asymmetric Oxidative Coupling between C(sp3)−H Bonds and Carboxylic Acids.

J. Am. Chem. Soc. 2025;
147: 627-635
DOI: 10.1021/jacs.4c12544
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Keywords

carboxylic acids - chiral esters - copper catalysis - C(sp3)−H bond oxidation

Significance

An asymmetric oxidative coupling between allylic or propargylic C(sp3)−H bonds with carboxylic acids under copper catalysis is reported. This mild procedure provides access to highly enantioenriched allylic or propargylic esters with good functional group tolerance.


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Comment

Mechanistic studies including DFT calculations support the shown mechanism. The addition of NaBArF 4 is crucial for the efficiency of this reaction, as the weakly coordinating BArF 4 – counteranion generates a vacant site at the copper(I) catalyst and lowers the overall energy barrier.


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Publication History

Article published online:
25 February 2025

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