Arylcarboxylation of Unactivated Alkenes with CO Via Visible-light Photoredox Catalysis

Overview

Journal Nat Commun

Specialty Biology

Date 2023 Jun 14

PMID 37316537

Authors

Wei Zhang

Zhen Chen

Yuan-Xu Jiang

Li-Li Liao

Wei Wang

Jian-Heng Ye

Da-Gang Yu

Affiliations

Soon will be listed here.

Abstract

Photocatalytic carboxylation of alkenes with CO is a promising and sustainable strategy to synthesize high value-added carboxylic acids. However, it is challenging and rarely investigated for unactivated alkenes due to their low reactivities. Herein, we report a visible-light photoredox-catalyzed arylcarboxylation of unactivated alkenes with CO, delivering a variety of tetrahydronaphthalen-1-ylacetic acids, indan-1-ylacetic acids, indolin-3-ylacetic acids, chroman-4-ylacetic acids and thiochroman-4-ylacetic acids in moderate-to-good yields. This reaction features high chemo- and regio-selectivities, mild reaction conditions (1 atm, room temperature), broad substrate scope, good functional group compatibility, easy scalability and facile derivatization of products. Mechanistic studies indicate that in situ generation of carbon dioxide radical anion and following radical addition to unactivated alkenes might be involved in the process.

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References

Seo H, Katcher M, Jamison T . Photoredox activation of carbon dioxide for amino acid synthesis in continuous flow. Nat Chem. 2017; 9(5):453-456. PMC: 5407320. DOI: 10.1038/nchem.2690. View

Liao L, Cao G, Jiang Y, Jin X, Hu X, Chruma J . α-Amino Acids and Peptides as Bifunctional Reagents: Carbocarboxylation of Activated Alkenes via Recycling CO. J Am Chem Soc. 2021; 143(7):2812-2821. DOI: 10.1021/jacs.0c11896. View

Zhang J, Li Y, Zhang F, Hu C, Chen Y . Generation of Alkoxyl Radicals by Photoredox Catalysis Enables Selective C(sp(3))-H Functionalization under Mild Reaction Conditions. Angew Chem Int Ed Engl. 2015; 55(5):1872-5. DOI: 10.1002/anie.201510014. View

Murata K, Numasawa N, Shimomaki K, Takaya J, Iwasawa N . Construction of a visible light-driven hydrocarboxylation cycle of alkenes by the combined use of Rh(i) and photoredox catalysts. Chem Commun (Camb). 2017; 53(21):3098-3101. DOI: 10.1039/c7cc00678k. View

Wu Z, Ren R, Zhu C . Combination of a Cyano Migration Strategy and Alkene Difunctionalization: The Elusive Selective Azidocyanation of Unactivated Olefins. Angew Chem Int Ed Engl. 2016; 55(36):10821-4. DOI: 10.1002/anie.201605130. View

Jiang Y, Chen L, Ran C, Song L, Zhang W, Liao L . Visible-Light Photoredox-Catalyzed Ring-Opening Carboxylation of Cyclic Oxime Esters with CO. ChemSusChem. 2020; 13(23):6312-6317. DOI: 10.1002/cssc.202002032. View

Jin Y, Caner J, Nishikawa S, Toriumi N, Iwasawa N . Catalytic direct hydrocarboxylation of styrenes with CO and H. Nat Commun. 2022; 13(1):7584. PMC: 9732006. DOI: 10.1038/s41467-022-35293-3. View

Jeon J, He Y, Shin S, Hong S . Visible-Light-Induced ortho-Selective Migration on Pyridyl Ring: Trifluoromethylative Pyridylation of Unactivated Alkenes. Angew Chem Int Ed Engl. 2019; 59(1):281-285. DOI: 10.1002/anie.201912746. View

van Vliet L, Rodenhuis N, Dijkstra D, Wikstrom H, Pugsley T, Serpa K . Synthesis and pharmacological evaluation of thiopyran analogues of the dopamine D3 receptor-selective agonist (4aR,10bR)-(+)-trans-3,4,4a,10b-tetrahydro-4-n-propyl-2H,5H [1]b enzopyrano[4,3-b]-1,4-oxazin-9-ol (PD 128907). J Med Chem. 2000; 43(15):2871-82. DOI: 10.1021/jm0000113. View

10.

Huang C, Li J, Liu W, Li C . Diacetyl as a "traceless" visible light photosensitizer in metal-free cross-dehydrogenative coupling reactions. Chem Sci. 2019; 10(19):5018-5024. PMC: 6530541. DOI: 10.1039/c8sc05631e. View

11.

Chen W, Liu Z, Tian J, Li J, Ma J, Cheng X . Building Congested Ketone: Substituted Hantzsch Ester and Nitrile as Alkylation Reagents in Photoredox Catalysis. J Am Chem Soc. 2016; 138(38):12312-5. DOI: 10.1021/jacs.6b06379. View

12.

Huihui K, Caputo J, Melchor Z, Olivares A, Spiewak A, Johnson K . Decarboxylative Cross-Electrophile Coupling of N-Hydroxyphthalimide Esters with Aryl Iodides. J Am Chem Soc. 2016; 138(15):5016-9. PMC: 4841236. DOI: 10.1021/jacs.6b01533. View

13.

Fischer H, Radom L . Factors Controlling the Addition of Carbon-Centered Radicals to Alkenes-An Experimental and Theoretical Perspective. Angew Chem Int Ed Engl. 2001; 40(8):1340-1371. DOI: 10.1002/1521-3773(20010417)40:8<1340::aid-anie1340>3.0.co;2-#. View

14.

Zhang L, Li Z, Takimoto M, Hou Z . Carboxylation Reactions with Carbon Dioxide Using N-Heterocyclic Carbene-Copper Catalysts. Chem Rec. 2019; 20(6):494-512. DOI: 10.1002/tcr.201900060. View

15.

Domingo L, Perez P . Global and local reactivity indices for electrophilic/nucleophilic free radicals. Org Biomol Chem. 2013; 11(26):4350-8. DOI: 10.1039/c3ob40337h. View

16.

Wu X, Zhu C . Radical-Mediated Remote Functional Group Migration. Acc Chem Res. 2020; 53(8):1620-1636. DOI: 10.1021/acs.accounts.0c00306. View

17.

Meng Q, Wang S, Huff G, Konig B . Ligand-Controlled Regioselective Hydrocarboxylation of Styrenes with CO by Combining Visible Light and Nickel Catalysis. J Am Chem Soc. 2018; 140(9):3198-3201. DOI: 10.1021/jacs.7b13448. View

18.

Chadha N, Silakari O . Indoles as therapeutics of interest in medicinal chemistry: Bird's eye view. Eur J Med Chem. 2017; 134:159-184. DOI: 10.1016/j.ejmech.2017.04.003. View

19.

Fu Q, Bo Z, Ye J, Ju T, Huang H, Liao L . Transition metal-free phosphonocarboxylation of alkenes with carbon dioxide via visible-light photoredox catalysis. Nat Commun. 2019; 10(1):3592. PMC: 6689110. DOI: 10.1038/s41467-019-11528-8. View

20.

Wu Z, Wang D, Liu Y, Huan L, Zhu C . Chemo- and Regioselective Distal Heteroaryl ipso-Migration: A General Protocol for Heteroarylation of Unactivated Alkenes. J Am Chem Soc. 2017; 139(4):1388-1391. DOI: 10.1021/jacs.6b11234. View