Issue 18, 2023

Polyhaloalkanes as the C1 source: radical-mediated migratory carbonylation of alkenes with polyhaloalkanes toward α,β-unsaturated carbonyls

Abstract

An unprecedented copper-promoted radical-mediated alkenyl C(sp2)–H carbonylation of alkenes with polyhaloalkanes for divergently producing α,β-unsaturated esters and aldehydes is presented. Employing polyhaloalkanes as the carbonyl C1 sources enables the carbonylation of the alkenyl C(sp2)–H bonds via a polyhaloalkyl radical addition, alkene alkoxypolyhaloalkylation and carbonylation cascade and provides general, stereoselective, and chemodivergent access to α,β-unsaturated esters and aldehydes relying on the nucleophile choice. Experimental mechanistic studies and DFT calculations indicate that transformation of polyhaloalkanes into polyhaloalkyl C(sp3)-centered radicals by single electron transfer of the in situ aryl radicals from aryl diazonium salts is crucial, and this process represents a new radical-mediated pathway featuring polyhaloalkyl radical addition across alkenes to generate the key 1-alkoxyl-2-polyhaloalkyl alkane intermediate followed by thermodynamic alkoxy-migratory carbonylation.

Graphical abstract: Polyhaloalkanes as the C1 source: radical-mediated migratory carbonylation of alkenes with polyhaloalkanes toward α,β-unsaturated carbonyls

Supplementary files

Article information

Article type
Research Article
Submitted
17 Jul 2023
Accepted
05 Aug 2023
First published
07 Aug 2023

Org. Chem. Front., 2023,10, 4670-4678

Polyhaloalkanes as the C1 source: radical-mediated migratory carbonylation of alkenes with polyhaloalkanes toward α,β-unsaturated carbonyls

T. Zhang, Y. Yao, J. Qin, Q. Sun, A. Li, Q. He, J. Li and X. Ouyang, Org. Chem. Front., 2023, 10, 4670 DOI: 10.1039/D3QO01100C

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