Nickel Catalysis Enables Convergent Paired Electrolysis for Direct Arylation of Benzylic C-H Bonds

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2021 Jun 7

PMID 34094332

Citations 16

Authors

Lei Zhang

Xile Hu

Affiliations

Soon will be listed here.

Abstract

Convergent paired electrosynthesis is an energy-efficient approach in organic synthesis; however, it is limited by the difficulty to match the innate redox properties of reaction partners. Here we use nickel catalysis to cross-couple the two intermediates generated at the two opposite electrodes of an electrochemical cell, achieving direct arylation of benzylic C-H bonds. This method yields a diverse set of diarylmethanes, which are important structural motifs in medicinal and materials chemistry. Preliminary mechanistic study suggests oxidation of a benzylic C-H bond, Ni-catalyzed C-C coupling, and reduction of a Ni intermediate as key elements of the catalytic cycle.

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References

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

Mohle S, Zirbes M, Rodrigo E, Gieshoff T, Wiebe A, Waldvogel S . Modern Electrochemical Aspects for the Synthesis of Value-Added Organic Products. Angew Chem Int Ed Engl. 2018; 57(21):6018-6041. PMC: 6001547. DOI: 10.1002/anie.201712732. 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

Perkins R, Pedro D, Hansen E . Electrochemical Nickel Catalysis for Sp-Sp Cross-Electrophile Coupling Reactions of Unactivated Alkyl Halides. Org Lett. 2017; 19(14):3755-3758. DOI: 10.1021/acs.orglett.7b01598. View

Wang H, Gao X, Lv Z, Abdelilah T, Lei A . Recent Advances in Oxidative R-H/R-H Cross-Coupling with Hydrogen Evolution via Photo-/Electrochemistry. Chem Rev. 2019; 119(12):6769-6787. DOI: 10.1021/acs.chemrev.9b00045. View

Kawamata Y, Vantourout J, Hickey D, Bai P, Chen L, Hou Q . Electrochemically Driven, Ni-Catalyzed Aryl Amination: Scope, Mechanism, and Applications. J Am Chem Soc. 2019; 141(15):6392-6402. PMC: 6996791. DOI: 10.1021/jacs.9b01886. View

Jiao K, Liu D, Ma H, Qiu H, Fang P, Mei T . Nickel-Catalyzed Electrochemical Reductive Relay Cross-Coupling of Alkyl Halides to Aryl Halides. Angew Chem Int Ed Engl. 2019; 59(16):6520-6524. DOI: 10.1002/anie.201912753. View

Vasilopoulos A, Zultanski S, Stahl S . Feedstocks to Pharmacophores: Cu-Catalyzed Oxidative Arylation of Inexpensive Alkylarenes Enabling Direct Access to Diarylalkanes. J Am Chem Soc. 2017; 139(23):7705-7708. DOI: 10.1021/jacs.7b03387. View

Liu D, Ma H, Fang P, Mei T . Nickel-Catalyzed Thiolation of Aryl Halides and Heteroaryl Halides through Electrochemistry. Angew Chem Int Ed Engl. 2019; 58(15):5033-5037. DOI: 10.1002/anie.201900956. View

10.

Wiebe A, Gieshoff T, Mohle S, Rodrigo E, Zirbes M, Waldvogel S . Electrifying Organic Synthesis. Angew Chem Int Ed Engl. 2018; 57(20):5594-5619. PMC: 5969240. DOI: 10.1002/anie.201711060. View

11.

Jiang H, Sha S, Jeong S, Manor B, Walsh P . Ni(NIXANTPHOS)-Catalyzed Mono-Arylation of Toluenes with Aryl Chlorides and Bromides. Org Lett. 2019; 21(6):1735-1739. DOI: 10.1021/acs.orglett.9b00294. View

12.

Zhang W, Chen P, Liu G . Copper-Catalyzed Arylation of Benzylic C-H bonds with Alkylarenes as the Limiting Reagents. J Am Chem Soc. 2017; 139(23):7709-7712. DOI: 10.1021/jacs.7b03781. View

13.

Li H, Breen C, Seo H, Jamison T, Fang Y, Bio M . Ni-Catalyzed Electrochemical Decarboxylative C-C Couplings in Batch and Continuous Flow. Org Lett. 2018; 20(5):1338-1341. PMC: 5838802. DOI: 10.1021/acs.orglett.8b00070. View

14.

Durandetti M, Nedelec J, Perichon J . Nickel-Catalyzed Direct Electrochemical Cross-Coupling between Aryl Halides and Activated Alkyl Halides. J Org Chem. 1996; 61(5):1748-1755. DOI: 10.1021/jo9518314. View

15.

Shen Y, Gu Y, Martin R . sp C-H Arylation and Alkylation Enabled by the Synergy of Triplet Excited Ketones and Nickel Catalysts. J Am Chem Soc. 2018; 140(38):12200-12209. DOI: 10.1021/jacs.8b07405. View

16.

Wang S, Zhang C, Shu Y, Jiang S, Xia Q, Chen L . Layered microporous polymers by solvent knitting method. Sci Adv. 2017; 3(3):e1602610. PMC: 5376128. DOI: 10.1126/sciadv.1602610. View

17.

Morales-Guio C, Liardet L, Hu X . Oxidatively Electrodeposited Thin-Film Transition Metal (Oxy)hydroxides as Oxygen Evolution Catalysts. J Am Chem Soc. 2016; 138(28):8946-57. DOI: 10.1021/jacs.6b05196. View

18.

Long Y, Jiang X, Dayam R, Sanchez T, Shoemaker R, Sei S . Rational design and synthesis of novel dimeric diketoacid-containing inhibitors of HIV-1 integrase: implication for binding to two metal ions on the active site of integrase. J Med Chem. 2004; 47(10):2561-73. DOI: 10.1021/jm030559k. View

19.

Bai Y, Liu N, Wang S, Wang S, Ning S, Shi L . Nickel-Catalyzed Electrochemical Phosphorylation of Aryl Bromides. Org Lett. 2019; 21(17):6835-6838. DOI: 10.1021/acs.orglett.9b02475. View

20.

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