Ni-Catalyzed Electrochemical Decarboxylative C-C Couplings in Batch and Continuous Flow

Overview

Journal Org Lett

Publisher American Chemical Society

Specialties Biochemistry
Chemistry

Date 2018 Feb 13

PMID 29431449

Citations 42

Authors

Hui Li

Christopher P Breen

Hyowon Seo

Timothy F Jamison

Yuan-Qing Fang

Matthew M Bio

Affiliations

Soon will be listed here.

Abstract

An electrochemically driven, nickel-catalyzed reductive coupling of N-hydroxyphthalimide esters with aryl halides is reported. The reaction proceeds under mild conditions in a divided electrochemical cell and employs a tertiary amine as the reductant. This decarboxylative C(sp)-C(sp) bond-forming transformation exhibits excellent substrate generality and functional group compatibility. An operationally simple continuous-flow version of this transformation using a commercial electrochemical flow reactor represents a robust and scalable synthesis of value added coupling process.

Citing Articles

Enantioselective reductive cross-couplings to forge C(sp)-C(sp) bonds by merging electrochemistry with nickel catalysis.

Wang Y, Sun B, Guo J, Zhu X, Gu Y, Han Y Nat Commun. 2025; 16(1):1108.

PMID: 39875390 PMC: 11775263. DOI: 10.1038/s41467-025-56377-w.

The Future of Electro-organic Synthesis in Drug Discovery and Early Development.

Stephen H, Rockl J ACS Org Inorg Au. 2024; 4(6):571-578.

PMID: 39649998 PMC: 11621954. DOI: 10.1021/acsorginorgau.4c00068.

Electrochemical Glycosylation via Halogen-Atom-Transfer for -Glycoside Assembly.

Wu J, Purushothaman R, Kallert F, Homolle S, Ackermann L ACS Catal. 2024; 14(15):11532-11544.

PMID: 39114086 PMC: 11301629. DOI: 10.1021/acscatal.4c02322.

Homogeneous Organic Reductant Based on 4,4'-Bu-2,2'-Bipyridine for Cross-Electrophile Coupling.

Charboneau D, Huang H, Barth E, Deziel A, Germe C, Hazari N Tetrahedron Lett. 2024; 145.

PMID: 39036418 PMC: 11258959. DOI: 10.1016/j.tetlet.2024.155159.

Mechanisms for radical reactions initiating from -hydroxyphthalimide esters.

Azpilcueta-Nicolas C, Lumb J Beilstein J Org Chem. 2024; 20:346-378.

PMID: 38410775 PMC: 10896223. DOI: 10.3762/bjoc.20.35.

References

Tasker S, Standley E, Jamison T . Recent advances in homogeneous nickel catalysis. Nature. 2014; 509(7500):299-309. PMC: 4344729. DOI: 10.1038/nature13274. View

Fu G . Transition-Metal Catalysis of Nucleophilic Substitution Reactions: A Radical Alternative to S1 and S2 Processes. ACS Cent Sci. 2017; 3(7):692-700. PMC: 5532721. DOI: 10.1021/acscentsci.7b00212. View

Pletcher D, Green R, Brown R . Flow Electrolysis Cells for the Synthetic Organic Chemistry Laboratory. Chem Rev. 2017; 118(9):4573-4591. DOI: 10.1021/acs.chemrev.7b00360. View

Zuo Z, Ahneman D, Chu L, Terrett J, Doyle A, MacMillan D . Dual catalysis. Merging photoredox with nickel catalysis: coupling of α-carboxyl sp³-carbons with aryl halides. Science. 2014; 345(6195):437-40. PMC: 4296524. DOI: 10.1126/science.1255525. View

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

Wang X, Wang S, Xue W, Gong H . Nickel-Catalyzed Reductive Coupling of Aryl Bromides with Tertiary Alkyl Halides. J Am Chem Soc. 2015; 137(36):11562-5. DOI: 10.1021/jacs.5b06255. 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

Anka-Lufford L, Huihui K, Gower N, Ackerman L, Weix D . Nickel-Catalyzed Cross-Electrophile Coupling with Organic Reductants in Non-Amide Solvents. Chemistry. 2016; 22(33):11564-7. DOI: 10.1002/chem.201602668. View

Edwards J, Merchant R, McClymont K, Knouse K, Qin T, Malins L . Decarboxylative alkenylation. Nature. 2017; 545(7653):213-218. PMC: 5478194. DOI: 10.1038/nature22307. View

10.

Paul A, Smith M, Vannucci A . Photoredox-Assisted Reductive Cross-Coupling: Mechanistic Insight into Catalytic Aryl-Alkyl Cross-Couplings. J Org Chem. 2017; 82(4):1996-2003. DOI: 10.1021/acs.joc.6b02830. View

11.

Xiong P, Xu H, Xu H . Metal- and Reagent-Free Intramolecular Oxidative Amination of Tri- and Tetrasubstituted Alkenes. J Am Chem Soc. 2017; 139(8):2956-2959. DOI: 10.1021/jacs.7b01016. View

12.

Kawamata Y, Yan M, Liu Z, Bao D, Chen J, Starr J . Scalable, Electrochemical Oxidation of Unactivated C-H Bonds. J Am Chem Soc. 2017; 139(22):7448-7451. PMC: 5465511. DOI: 10.1021/jacs.7b03539. View

13.

Jana R, Pathak T, Sigman M . Advances in transition metal (Pd, Ni, Fe)-catalyzed cross-coupling reactions using alkyl-organometallics as reaction partners. Chem Rev. 2011; 111(3):1417-92. PMC: 3075866. DOI: 10.1021/cr100327p. View

14.

Candish L, Teders M, Glorius F . Transition-Metal-Free, Visible-Light-Enabled Decarboxylative Borylation of Aryl N-Hydroxyphthalimide Esters. J Am Chem Soc. 2017; 139(22):7440-7443. DOI: 10.1021/jacs.7b03127. View

15.

Toriyama F, Cornella J, Wimmer L, Chen T, Dixon D, Creech G . Redox-Active Esters in Fe-Catalyzed C-C Coupling. J Am Chem Soc. 2016; 138(35):11132-5. PMC: 5016806. DOI: 10.1021/jacs.6b07172. View

16.

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

17.

Sambiagio C, Sterckx H, Maes B . Electrosynthesis: A New Frontier in Aerobic Oxidation?. ACS Cent Sci. 2017; 3(7):686-688. PMC: 5532737. DOI: 10.1021/acscentsci.7b00275. View

18.

Qin T, Cornella J, Li C, Malins L, Edwards J, Kawamura S . A general alkyl-alkyl cross-coupling enabled by redox-active esters and alkylzinc reagents. Science. 2016; 352(6287):801-5. PMC: 4867118. DOI: 10.1126/science.aaf6123. View

19.

Fu N, Sauer G, Lin S . Electrocatalytic Radical Dichlorination of Alkenes with Nucleophilic Chlorine Sources. J Am Chem Soc. 2017; 139(43):15548-15553. DOI: 10.1021/jacs.7b09388. View

20.

Yang Q, Li Y, Ma C, Fang P, Zhang X, Mei T . Palladium-Catalyzed C(sp)-H Oxygenation via Electrochemical Oxidation. J Am Chem Soc. 2017; 139(8):3293-3298. DOI: 10.1021/jacs.7b01232. View