Dehydrogenative Coupling Reactions with Guanidino-Functionalized Aromatics

Overview

Journal Chemistry

Specialty Chemistry

Date 2024 Oct 7

PMID 39370772

Authors

Petra Walter

Maximilian Schulz

Olaf Hubner

Andrei Poddelskii

Elisabeth Kaifer

Hans-Jorg Himmel

Affiliations

Soon will be listed here.

Abstract

Dehydrogenative coupling (DC) reactions are of importance for the construction of new carbon-element bonds in synthetic organic chemistry. In this work, we report on the synthesis and characterization of several redox-active guanidino-functionalized aromatic molecules (GFAs) for use in DC (C-C and C-O) reactions. In a systematic approach, we first characterize the new DC reagents in all relevant redox and protonation states, and compare their performance in competitive test proton-coupled electron transfer (PCET) reactions. Then, their use in four different DC reactions with different mechanisms is evaluated.

Citing Articles

Dehydrogenative Coupling Reactions with Guanidino-Functionalized Aromatics.

Walter P, Schulz M, Hubner O, Poddelskii A, Kaifer E, Himmel H Chemistry. 2024; 30(71):e202402917.

PMID: 39370772 PMC: 11653247. DOI: 10.1002/chem.202402917.

References

Pannwitz A, Wenger O . Recent advances in bioinspired proton-coupled electron transfer. Dalton Trans. 2018; 48(18):5861-5868. DOI: 10.1039/c8dt04373f. View

Wang W, Wang Q, He X, Shen Y, Zhai Z, Zhang R . Electrochemical Continuous-Flow Scholl Reaction toward Polycyclic Aromatic Hydrocarbons. Org Lett. 2024; 26(11):2243-2248. DOI: 10.1021/acs.orglett.4c00445. View

Maskey R, Bendel C, Malzacher J, Greb L . Completing the Redox-Series of Silicon Trisdioxolene: ortho-Quinone and Lewis Superacid Make a Powerful Redox Catalyst. Chemistry. 2020; 26(72):17386-17389. PMC: 7839739. DOI: 10.1002/chem.202004712. View

Wenger O . Proton-coupled electron transfer originating from excited states of luminescent transition-metal complexes. Chemistry. 2011; 17(42):11692-702. DOI: 10.1002/chem.201102011. View

Wenger O . Proton-coupled electron transfer with photoexcited metal complexes. Acc Chem Res. 2013; 46(7):1517-26. DOI: 10.1021/ar300289x. View

Li M . C3-C3' and C6-C6' Oxidative Couplings of Carbazoles. Chemistry. 2018; 25(5):1142-1151. DOI: 10.1002/chem.201803246. View

Hirano K, Miura M . Copper-mediated oxidative direct C-C (hetero)aromatic cross-coupling. Chem Commun (Camb). 2012; 48(87):10704-14. DOI: 10.1039/c2cc34659a. View

Li C . Cross-dehydrogenative coupling (CDC): exploring C-C bond formations beyond functional group transformations. Acc Chem Res. 2009; 42(2):335-44. DOI: 10.1021/ar800164n. View

Weigend F . Accurate Coulomb-fitting basis sets for H to Rn. Phys Chem Chem Phys. 2006; 8(9):1057-65. DOI: 10.1039/b515623h. View

10.

Zhai L, Shukla R, Wadumethrige S, Rathore R . Probing the arenium-ion (protontransfer) versus the cation-radical (electron transfer) mechanism of Scholl reaction using DDQ as oxidant. J Org Chem. 2010; 75(14):4748-60. DOI: 10.1021/jo100611k. View

11.

Wild U, Hubner O, Himmel H . Redox-Active Guanidines in Proton-Coupled Electron-Transfer Reactions: Real Alternatives to Benzoquinones?. Chemistry. 2019; 25(70):15988-15992. PMC: 7065378. DOI: 10.1002/chem.201903438. View

12.

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

13.

Agarwal R, Coste S, Groff B, Heuer A, Noh H, Parada G . Free Energies of Proton-Coupled Electron Transfer Reagents and Their Applications. Chem Rev. 2021; 122(1):1-49. PMC: 9175307. DOI: 10.1021/acs.chemrev.1c00521. View

14.

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

15.

Camargo Solorzano P, Baumgartner M, Puiatti M, Jimenez L . Arenium cation or radical cation? An insight into the cyclodehydrogenation reaction of 2-substituted binaphthyls mediated by Lewis acids. RSC Adv. 2022; 10(37):21974-21985. PMC: 9054548. DOI: 10.1039/d0ra04213g. View

16.

Wirtanen T, Aikonen S, Muuronen M, Melchionna M, Kemell M, Davodi F . Carbocatalytic Oxidative Dehydrogenative Couplings of (Hetero)Aryls by Oxidized Multi-Walled Carbon Nanotubes in Liquid Phase. Chemistry. 2019; 25(53):12288-12293. DOI: 10.1002/chem.201903054. View

17.

Liu C, Zhang H, Shi W, Lei A . Bond formations between two nucleophiles: transition metal catalyzed oxidative cross-coupling reactions. Chem Rev. 2011; 111(3):1780-824. DOI: 10.1021/cr100379j. View

18.

Turek A, Hardee D, Ullman A, Nocera D, Jacobsen E . Activation of Electron-Deficient Quinones through Hydrogen-Bond-Donor-Coupled Electron Transfer. Angew Chem Int Ed Engl. 2015; 55(2):539-44. PMC: 5120606. DOI: 10.1002/anie.201508060. View

19.

Beccalli E, Broggini G, Martinelli M, Sottocornola S . C-C, C-O, C-N bond formation on sp2 carbon by Pd(II)-catalyzed reactions involving oxidant agents. Chem Rev. 2007; 107(11):5318-65. DOI: 10.1021/cr068006f. View

20.

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