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Synfacts 2025; 21(01): 44
DOI: 10.1055/a-2467-5968
DOI: 10.1055/a-2467-5968
Metals in Synthesis
Asymmetric Allylic C(sp3)–H Acyloxylation of Internal Alkenes Enabled by Photoexcited Copper Catalysis
Tang S,
Xu H,
Dang Y *,
Yu S *.
Tianjin University and Nanjing University, P. R. China
Photoexcited Copper-Catalyzed Enantioselective Allylic C(sp3)–H Acyloxylation of Acyclic Internal Alkenes.
J. Am. Chem. Soc. 2024;
146: 27196-27203
DOI: 10.1021/jacs.4c11145
Photoexcited Copper-Catalyzed Enantioselective Allylic C(sp3)–H Acyloxylation of Acyclic Internal Alkenes.
J. Am. Chem. Soc. 2024;
146: 27196-27203
DOI: 10.1021/jacs.4c11145
Keywords
acyloxylation - allylic C(sp3)–H functionalization - copper catalysis - Kharasch–Sosnovsky oxidation - photoexcited catalysis
Significance
A visible-light-driven, copper-catalyzed enantio- and regioselective Kharasch–Sosnovsky-type allylic C(sp3)–H acyloxylation of internal alkenes is reported. This mild protocol features a broad substrate scope and provides direct access to enantioenriched allylic esters.
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Comment
Mechanistic studies including DFT calculations support the shown mechanism. Notably, either the peroxy ester or the carboxylic acid can be employed, with the latter requiring the addition of one equivalent of di-tert-butyl peroxide (DTBP) as the oxidant.
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Publication History
Article published online:
20 December 2024
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