In:
Angewandte Chemie, Wiley, Vol. 135, No. 23 ( 2023-06-05)
Abstract:
Carboxylation of easily available alkenes with CO 2 is highly important to afford value‐added carboxylic acids. Although dicarboxylation of activated alkenes, especially 1,3‐dienes, has been widely investigated, the challenging dicarboxylation of unactivated 1, n ‐dienes ( n 〉 3) with CO 2 remains unexplored. Herein, we report the first dicarboxylation of unactivated skipped dienes with CO 2 via electrochemistry, affording valuable dicarboxylic acids. Control experiments and DFT calculations support the single electron transfer (SET) reduction of CO 2 to its radical anion, which is followed by sluggish radical addition to unactivated alkenes, SET reduction of unstabilized alkyl radicals to carbanions and nucleophilic attack on CO 2 to give desired products. This reaction features mild reaction conditions, broad substrate scope, facile derivations of products and promising application in polymer chemistry.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v135.23
DOI:
10.1002/ange.202301892
Language:
English
Publisher:
Wiley
Publication Date:
2023
detail.hit.zdb_id:
506609-8
detail.hit.zdb_id:
1479266-7