PDF icon Download PDF
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
CrossrefPubMedSearch in Google Scholar
› Further Information
 
 PDF Download Permissions and Reprints

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.


 

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.


 

 

Publication History

Article published online:
25 February 2025

© 2025. Thieme. All rights reserved.

Georg Thieme Verlag KG
Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany


  Permissions and Reprints