We found a match
Your institution may have access to this item. Find your institution then sign in to continue.
- Title
An Electrocatalytic Cascade Reaction for the Synthesis of Ketones Using CO<sub>2</sub> as a CO Surrogate.
- Authors
Sheta, Ahmed M.; Fernández, Sergio; Liu, Changwei; Dubed‐Bandomo, Geyla C.; Lloret‐Fillol, Julio
- Abstract
The construction of carbonyl compounds via carbonylation reactions using safe CO sources remains a long‐standing challenge to synthetic chemists. Herein, we propose a catalyst cascade Scheme in which CO2 is used as a CO surrogate in the carbonylation of benzyl chlorides. Our approach is based on the cooperation between two coexisting catalytic cycles: the CO2‐to‐CO electroreduction cycle promoted by [Fe(TPP)Cl] (TPP=meso‐tetraphenylporphyrin) and an electrochemical carbonylation cycle catalyzed by [Ni(bpy)Br2] (2,2′‐bipyridine). As a proof of concept, this protocol allows for the synthesis of symmetric ketones from good to excellent yields in an undivided cell with non‐sacrificial electrodes. The reaction can be directly scaled up to gram‐scale and operates effectively at a CO2 concentration of 10 %, demonstrating its robustness. Our mechanistic studies based on cyclic voltammetry, IR spectroelectrochemistry and Density Functional Theory calculations suggest a synergistic effect between the two catalysts. The CO produced from CO2 reduction is key in the formation of the [Ni(bpy)(CO)2], which is proposed as the catalytic intermediate responsible for the C−C bond formation in the carbonylation steps.
- Subjects
CARBONYLATION; BENZYL chloride; DENSITY functional theory; KETONES; CYCLIC voltammetry; CARBONYL compounds
- Publication
Angewandte Chemie, 2024, Vol 136, Issue 23, p1
- ISSN
0044-8249
- Publication type
Academic Journal
- DOI
10.1002/ange.202403674