Substrate-controlled C-H or C-C Alkynylation of Cyclopropanes: Generation of Aryl Radical Cations by Direct Light Activation of Hypervalent Iodine Reagents

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2022 Dec 15

PMID 36519037

Authors

Tin V T Nguyen

Matthew D Wodrich

Jerome Waser

Affiliations

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Abstract

We report the first oxidative C-H alkynylation of arylcyclopropanes. Irradiation of ethynylbenziodoxolone (EBX) reagents with visible light at 440 nm promoted the reaction. By the choice of the aryl group on the cyclopropane, it was possible to completely switch the outcome of the reaction from the alkynylation of the C-H bond to the oxyalkynylation of the C-C bond, which proceeded without the need for a catalyst, in contrast to previous works. The oxyalkynylation could also be extended to aminocyclopropanes as well as styrenes. Computations indicated that the C-H activation became a favoured nearly barrierless process in the presence of two methyl groups on the benzene ring.

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References

Ilchenko N, Hedberg M, Szabo K . Fluorinative ring-opening of cyclopropanes by hypervalent iodine reagents. An efficient method for 1,3-oxyfluorination and 1,3-difluorination. Chem Sci. 2017; 8(2):1056-1061. PMC: 5356504. DOI: 10.1039/c6sc03471c. View

Nakajima M, Nagasawa S, Matsumoto K, Kuribara T, Muranaka A, Uchiyama M . A Direct S →T Transition in the Photoreaction of Heavy-Atom-Containing Molecules. Angew Chem Int Ed Engl. 2020; 59(17):6847-6852. DOI: 10.1002/anie.201915181. View

Tian Z, Fattahi A, Lis L, Kass S . Cycloalkane and cycloalkene C-H bond dissociation energies. J Am Chem Soc. 2006; 128(51):17087-92. DOI: 10.1021/ja065348u. View

Petzold D, Singh P, Almqvist F, Konig B . Visible-Light-Mediated Synthesis of β-Chloro Ketones from Aryl Cyclopropanes. Angew Chem Int Ed Engl. 2019; 58(25):8577-8580. DOI: 10.1002/anie.201902473. View

Amos S, Nicolai S, Waser J . Photocatalytic Umpolung of - and -substituted alkenes for the synthesis of 1,2-amino alcohols and diols. Chem Sci. 2021; 11(41):11274-11279. PMC: 8162387. DOI: 10.1039/d0sc03655b. View

Banik S, Mennie K, Jacobsen E . Catalytic 1,3-Difunctionalization via Oxidative C-C Bond Activation. J Am Chem Soc. 2017; 139(27):9152-9155. PMC: 5671765. DOI: 10.1021/jacs.7b05160. View

Wang D, Muck-Lichtenfeld C, Studer A . Hydrogen Atom Transfer Induced Boron Retaining Coupling of Organoboronic Esters and Organolithium Reagents. J Am Chem Soc. 2019; 141(36):14126-14130. PMC: 6756585. DOI: 10.1021/jacs.9b07960. View

Vidal M, Epshtein M, Scutelnic V, Yang Z, Xue T, Leone S . Interplay of Open-Shell Spin-Coupling and Jahn-Teller Distortion in Benzene Radical Cation Probed by X-ray Spectroscopy. J Phys Chem A. 2020; 124(46):9532-9541. DOI: 10.1021/acs.jpca.0c08732. View

Amos S, Cavalli D, Le Vaillant F, Waser J . Direct Photoexcitation of Ethynylbenziodoxolones: An Alternative to Photocatalysis for Alkynylation Reactions*. Angew Chem Int Ed Engl. 2021; 60(44):23827-23834. PMC: 8596672. DOI: 10.1002/anie.202110257. View

10.

Lu Z, Parrish J, Yoon T . [3+2] Photooxygenation of aryl cylopropanes via visible light photocatalysis. Tetrahedron. 2014; 70(27-28):4270-4278. PMC: 4142714. DOI: 10.1016/j.tet.2014.02.045. View

11.

Le Vaillant F, Courant T, Waser J . Room-temperature decarboxylative alkynylation of carboxylic acids using photoredox catalysis and EBX reagents. Angew Chem Int Ed Engl. 2015; 54(38):11200-4. DOI: 10.1002/anie.201505111. View

12.

Kim J, Sim M, Kim N, Hong S . Asymmetric C-H functionalization of cyclopropanes using an isoleucine-NH bidentate directing group. Chem Sci. 2018; 6(6):3611-3616. PMC: 5659170. DOI: 10.1039/c5sc01137j. View

13.

Zhou Q, Guo W, Ding W, Wu X, Chen X, Lu L . Decarboxylative alkynylation and carbonylative alkynylation of carboxylic acids enabled by visible-light photoredox catalysis. Angew Chem Int Ed Engl. 2015; 54(38):11196-9. DOI: 10.1002/anie.201504559. View

14.

Liu H, Li Y, Wang D, Sun M, Feng C . Visible-Light-Promoted Regioselective 1,3-Fluoroallylation of -Difluorocyclopropanes. Org Lett. 2020; 22(21):8681-8686. DOI: 10.1021/acs.orglett.0c03268. View

15.

Tsuji M . Most stable conformation of the cyclopropane ring attached at a carbon atom in a 1,2-dicarba-closo-dodecaborane(12) system. J Org Chem. 2004; 69(12):4063-74. DOI: 10.1021/jo049854i. View

16.

Li J, Huang Q, Wang S, Ji S . Trisulfur Radical Anion (S) Involved [1 + 2 + 2] and [1 + 3 + 1] Cycloaddition with Aromatic Alkynes: Synthesis of Tetraphenylthiophene and 2-Benzylidenetetrahydrothiophene Derivatives. Org Lett. 2018; 20(15):4704-4708. DOI: 10.1021/acs.orglett.8b02066. View

17.

Li G, Morales-Rivera C, Wang Y, Gao F, He G, Liu P . Photoredox-mediated Minisci C-H alkylation of -heteroarenes using boronic acids and hypervalent iodine. Chem Sci. 2017; 7(10):6407-6412. PMC: 5356021. DOI: 10.1039/c6sc02653b. View

18.

Tachikawa H . Jahn-Teller Effect of the Benzene Radical Cation: A Direct ab Initio Molecular Dynamics Study. J Phys Chem A. 2018; 122(16):4121-4129. DOI: 10.1021/acs.jpca.8b00292. View

19.

Walsh S, Severino A, Zhou C, He J, Liang G, Tan C . 3-Substituted 3-(4-aryloxyaryl)-propanoic acids as GPR40 agonists. Bioorg Med Chem Lett. 2011; 21(11):3390-4. DOI: 10.1016/j.bmcl.2011.03.114. View

20.

Kubota A, Sanford M . Palladium-Catalyzed Ligand-Directed Oxidative Functionalization of Cyclopropanes. Synthesis (Stuttg). 2015; 2011(16):2579-2589. PMC: 4386895. DOI: 10.1055/s-0030-1260087. View