Paired electrocatalysis unlocks cross-dehydrogenative coupling of C(sp 3 )-H bonds using a pentacoordinated cobalt-salen catalyst

Cross-dehydrogenative coupling of C(sp )-H bonds is an ideal approach for C(sp )-C(sp ) bond construction. However, conventional approaches mainly rely on a single activation mode by either stoichiometric oxidants or electrochemical oxidation, which would lead to inferior selectivity in the reaction...

Full description

Saved in:
Bibliographic Details
Published inNature communications Vol. 15; no. 1; p. 2897
Main Authors Liu, Ke, Lei, Mengna, Li, Xin, Zhang, Xuemei, Zhang, Ying, Fan, Weigang, Li, Man-Bo, Zhang, Sheng
Format Journal Article
LanguageEnglish
Published England Nature Publishing Group 04.04.2024
Nature Portfolio
Subjects
Bonding
Catalysis
Catalysts
Cobalt
Construction
Coupling
Dehydrogenation
Electrocatalysis
Electrochemical oxidation
Electrochemistry
Electrode potentials
Evolution
Functional groups
Hydrides
Hydrogen
Hydrogen evolution reactions
Oxidants
Oxidation
Oxidizing agents
Reaction mechanisms
Redox potential
Selectivity
Synergistic effect
Online AccessGet full text

Cover

More Information
Summary:Cross-dehydrogenative coupling of C(sp )-H bonds is an ideal approach for C(sp )-C(sp ) bond construction. However, conventional approaches mainly rely on a single activation mode by either stoichiometric oxidants or electrochemical oxidation, which would lead to inferior selectivity in the reaction between similar C(sp )-H bonds. Herein we describe our development of a paired electrocatalysis strategy to access an unconventional selectivity in the cross-dehydrogenative coupling of alcoholic α C(sp )-H with allylic (or benzylic) C-H bonds, which combines hydrogen evolution reaction catalysis with hydride transfer catalysis. To maximize the synergistic effect of the catalyst combinations, a HER catalyst pentacoordinated Co-salen is disclosed. The catalyst displays a large redox-potential gap (1.98 V) and suitable redox potential. With the optimized catalyst combination, an electrochemical cross-dehydrogenative coupling protocol features unconventional chemoselectivity (C-C vs. C-O coupling), excellent functional group tolerance (84 examples), valuable byproduct (hydrogen), and high regio- and site-selectivity. A plausible reaction mechanism is also proposed to rationalize the experimental observations.
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
ObjectType-Feature-2
content type line 23
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-024-47220-9