Paired Electrocatalysis Unlocks Cross-dehydrogenative Coupling of C(sp)-H Bonds Using a Pentacoordinated Cobalt-salen Catalyst

Overview

Journal Nat Commun

Specialty Biology

Date 2024 Apr 4

PMID 38575564

Authors

Ke Liu

Mengna Lei

Xin Li

Xuemei Zhang

Ying Zhang

Weigang Fan

Man-Bo Li

Sheng Zhang

Affiliations

Soon will be listed here.

Abstract

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.

References

Girard S, Knauber T, Li C . The cross-dehydrogenative coupling of C(sp3)-H bonds: a versatile strategy for C-C bond formations. Angew Chem Int Ed Engl. 2013; 53(1):74-100. DOI: 10.1002/anie.201304268. View

Zou L, Xiang S, Sun R, Lu Q . Selective C(sp)-H arylation/alkylation of alkanes enabled by paired electrocatalysis. Nat Commun. 2023; 14(1):7992. PMC: 10693613. DOI: 10.1038/s41467-023-43791-1. View

Yan M, Kawamata Y, Baran P . Synthetic Organic Electrochemical Methods Since 2000: On the Verge of a Renaissance. Chem Rev. 2017; 117(21):13230-13319. PMC: 5786875. DOI: 10.1021/acs.chemrev.7b00397. View

Nelson T, Blakey S . Intermolecular Allylic C-H Etherification of Internal Olefins. Angew Chem Int Ed Engl. 2018; 57(45):14911-14915. DOI: 10.1002/anie.201809863. View

Yuan Y, Lei A . Electrochemical Oxidative Cross-Coupling with Hydrogen Evolution Reactions. Acc Chem Res. 2019; 52(12):3309-3324. DOI: 10.1021/acs.accounts.9b00512. View

Wu T, Moeller K . Organic Electrochemistry: Expanding the Scope of Paired Reactions. Angew Chem Int Ed Engl. 2021; 60(23):12883-12890. DOI: 10.1002/anie.202100193. View

Li P, Kou G, Feng T, Wang M, Qiu Y . Electrochemical NiH-Catalyzed C(sp )-C(sp ) Coupling of Alkyl Halides and Alkyl Alkenes. Angew Chem Int Ed Engl. 2023; 62(44):e202311941. DOI: 10.1002/anie.202311941. View

Marinescu S, Winkler J, Gray H . Molecular mechanisms of cobalt-catalyzed hydrogen evolution. Proc Natl Acad Sci U S A. 2012; 109(38):15127-31. PMC: 3458341. DOI: 10.1073/pnas.1213442109. View

Jiang Y, Xu K, Zeng C . Use of Electrochemistry in the Synthesis of Heterocyclic Structures. Chem Rev. 2017; 118(9):4485-4540. DOI: 10.1021/acs.chemrev.7b00271. View

10.

Llorente M, Nguyen B, Kubiak C, Moeller K . Paired Electrolysis in the Simultaneous Production of Synthetic Intermediates and Substrates. J Am Chem Soc. 2016; 138(46):15110-15113. DOI: 10.1021/jacs.6b08667. View

11.

Zhang S, Findlater M . Electrochemically Driven Hydrogen Atom Transfer Catalysis: A Tool for C(sp)/Si-H Functionalization and Hydrofunctionalization of Alkenes. ACS Catal. 2023; 13(13):8731-8751. PMC: 10334887. DOI: 10.1021/acscatal.3c01221. View

12.

Zhang P, Sheng X, Chen X, Fang Z, Jiang J, Wang M . Paired Electrocatalytic Oxygenation and Hydrogenation of Organic Substrates with Water as the Oxygen and Hydrogen Source. Angew Chem Int Ed Engl. 2019; 58(27):9155-9159. PMC: 6617801. DOI: 10.1002/anie.201903936. View

13.

Chen M, Wu Z, Song J, Xu H . Electrocatalytic Allylic C-H Alkylation Enabled by a Dual-Function Cobalt Catalyst. Angew Chem Int Ed Engl. 2022; 61(14):e202115954. DOI: 10.1002/anie.202115954. View

14.

Xiong P, Xu H . Chemistry with Electrochemically Generated N-Centered Radicals. Acc Chem Res. 2019; 52(12):3339-3350. DOI: 10.1021/acs.accounts.9b00472. View

15.

Yang G, Jiao Y, Yan H, Xie Y, Tian C, Wu A . Unraveling the mechanism for paired electrocatalysis of organics with water as a feedstock. Nat Commun. 2022; 13(1):3125. PMC: 9170728. DOI: 10.1038/s41467-022-30495-1. View

16.

Rockl J, Pollok D, Franke R, Waldvogel S . A Decade of Electrochemical Dehydrogenative C,C-Coupling of Aryls. Acc Chem Res. 2019; 53(1):45-61. DOI: 10.1021/acs.accounts.9b00511. View

17.

Sauermann N, Meyer T, Tian C, Ackermann L . Electrochemical Cobalt-Catalyzed C-H Oxygenation at Room Temperature. J Am Chem Soc. 2017; 139(51):18452-18455. DOI: 10.1021/jacs.7b11025. View

18.

Moeller K . Using Physical Organic Chemistry To Shape the Course of Electrochemical Reactions. Chem Rev. 2018; 118(9):4817-4833. DOI: 10.1021/acs.chemrev.7b00656. View

19.

Francke R, Little R . Redox catalysis in organic electrosynthesis: basic principles and recent developments. Chem Soc Rev. 2014; 43(8):2492-521. DOI: 10.1039/c3cs60464k. View

20.

Waldvogel S, Lips S, Selt M, Riehl B, Kampf C . Electrochemical Arylation Reaction. Chem Rev. 2018; 118(14):6706-6765. DOI: 10.1021/acs.chemrev.8b00233. View