Silver-catalyzed Direct Selanylation of Indoles: Synthesis and Mechanistic Insights

Overview

Journal RSC Adv

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2023 Jan 23

PMID 36686957

Authors

Elise Ane Maluf Rios

Carla M B Gomes

Gabriel L Silverio

Eduardo Q Luz

Sher Ali

Caroline Da Ros Montes DOca

Breidi Albach

Renan B Campos

Daniel S Rampon

Affiliations

Soon will be listed here.

Abstract

Herein we describe the Ag(i)-catalyzed direct selanylation of indoles with diorganoyl diselenides. The reaction gave 3-selanylindoles with high regioselectivity and also allowed direct access to 2-selanylindoles when the C3 position of the indole ring was blocked a process similar to Plancher rearrangement. Experimental analyses and density functional theory calculations were carried out in order to picture the reaction mechanism. Among the pathways considered ( concerted metalation-deprotonation, Ag(iii), radical, and electrophilic aromatic substitution), our findings support a classic electrophilic aromatic substitution Lewis adducts between Ag(i) and diorganoyl diselenides. The results also afforded new insights into the interactions between Ag(i) and diorganoyl diselenides.

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References

Yamamoto T, Takimiya K . Facile synthesis of highly pi-extended heteroarenes, dinaphtho[2,3-b:2',3'-f]chalcogenopheno[3,2-b]chalcogenophenes, and their application to field-effect transistors. J Am Chem Soc. 2007; 129(8):2224-5. DOI: 10.1021/ja068429z. View

Thupyai A, Pimpasri C, Yotphan S . DABCO-catalyzed silver-promoted direct thiolation of pyrazolones with diaryl disulfides. Org Biomol Chem. 2017; 16(3):424-432. DOI: 10.1039/c7ob02860a. View

Azeredo J, Godoi M, Martins G, Silveira C, Braga A . A solvent- and metal-free synthesis of 3-chacogenyl-indoles employing DMSO/I2 as an eco-friendly catalytic oxidation system. J Org Chem. 2014; 79(9):4125-30. DOI: 10.1021/jo5000779. View

Jordan A, Lalic G, Sadighi J . Coinage Metal Hydrides: Synthesis, Characterization, and Reactivity. Chem Rev. 2016; 116(15):8318-72. DOI: 10.1021/acs.chemrev.6b00366. View

Alvarez-Corral M, Munoz-Dorado M, Rodriguez-Garcia I . Silver-mediated synthesis of heterocycles. Chem Rev. 2008; 108(8):3174-98. DOI: 10.1021/cr078361l. View

Huang D, Yu H, Wang T, Yang H, Yao R, Liang Z . Efficacy and safety of umifenovir for coronavirus disease 2019 (COVID-19): A systematic review and meta-analysis. J Med Virol. 2020; 93(1):481-490. PMC: 7361300. DOI: 10.1002/jmv.26256. View

Pyykko P . Theoretical chemistry of gold. Angew Chem Int Ed Engl. 2004; 43(34):4412-56. DOI: 10.1002/anie.200300624. View

Gao M, He C, Chen H, Bai R, Cheng B, Lei A . Synthesis of pyrroles by click reaction: silver-catalyzed cycloaddition of terminal alkynes with isocyanides. Angew Chem Int Ed Engl. 2013; 52(27):6958-61. DOI: 10.1002/anie.201302604. View

Guan S, Chen Y, Wu H, Xu R . Iron-catalyzed tandem reaction of C-Se bond coupling/selenosulfonation of indols with benzeneselenols. RSC Adv. 2022; 10(45):27058-27063. PMC: 9055526. DOI: 10.1039/d0ra05922f. View

10.

Liu Z, Liu J, Zhang L, Liao P, Song J, Bi X . Silver(I)-catalyzed hydroazidation of ethynyl carbinols: synthesis of 2-azidoallyl alcohols. Angew Chem Int Ed Engl. 2014; 53(21):5305-9. DOI: 10.1002/anie.201310264. View

11.

Halbes-Letinois U, Weibel J, Pale P . The organic chemistry of silver acetylides. Chem Soc Rev. 2007; 36(5):759-69. DOI: 10.1039/b602151b. View

12.

Diaz-Requejo M, Perez P . Coinage metal catalyzed C-H bond functionalization of hydrocarbons. Chem Rev. 2008; 108(8):3379-94. DOI: 10.1021/cr078364y. View

13.

Tan X, Song T, Wang Z, Chen H, Cui L, Li C . Silver-Catalyzed Decarboxylative Bromination of Aliphatic Carboxylic Acids. Org Lett. 2017; 19(7):1634-1637. DOI: 10.1021/acs.orglett.7b00439. View

14.

Birmann P, Sousa F, de Oliveira D, Domingues M, Vieira B, Lenardao E . 3-(4-Chlorophenylselanyl)-1-methyl-1H-indole, a new selenium compound elicits an antinociceptive and anti-inflammatory effect in mice. Eur J Pharmacol. 2018; 827:71-79. DOI: 10.1016/j.ejphar.2018.03.005. View

15.

Nogueira C, Barbosa N, Rocha J . Toxicology and pharmacology of synthetic organoselenium compounds: an update. Arch Toxicol. 2021; 95(4):1179-1226. PMC: 8012418. DOI: 10.1007/s00204-021-03003-5. View

16.

Fonseca S, Padilha N, Thurow S, Roehrs J, Savegnago L, de Souza M . Ultrasound-promoted copper-catalyzed synthesis of bis-arylselanyl chrysin derivatives with boosted antioxidant and anticancer activities. Ultrason Sonochem. 2017; 39:827-836. DOI: 10.1016/j.ultsonch.2017.06.007. View

17.

Bantreil X, Bourderioux A, Mateo P, Hagerman C, Selkti M, Brachet E . Phosphine-Triggered Selectivity Switch in Silver-Catalyzed o-Alkynylbenzohydroxamic Acid Cycloisomerizations. Org Lett. 2016; 18(19):4814-4817. DOI: 10.1021/acs.orglett.6b02235. View

18.

Naodovic M, Yamamoto H . Asymmetric silver-catalyzed reactions. Chem Rev. 2008; 108(8):3132-48. DOI: 10.1021/cr068413r. View

19.

Sivaguru P, Cao S, Babu K, Bi X . Silver-Catalyzed Activation of Terminal Alkynes for Synthesizing Nitrogen-Containing Molecules. Acc Chem Res. 2020; 53(3):662-675. DOI: 10.1021/acs.accounts.9b00623. View

20.

Freudendahl D, Santoro S, Shahzad S, Santi C, Wirth T . Green chemistry with selenium reagents: development of efficient catalytic reactions. Angew Chem Int Ed Engl. 2009; 48(45):8409-11. DOI: 10.1002/anie.200903893. View