Subscribe to RSS
DOI: 10.1055/s-0041-1737816
Generation of Thiyl Radicals from Air-Stable, Odorless Thiophenol Surrogates: Application to Visible-Light-Promoted C–S Cross-Coupling
This work was supported by the Engineering and Physical Sciences Research Council (EPSRC) Centre for Doctoral Training in Sustainable Chemistry (EP/S022236/1) through a Ph.D. studentship to C.S., and a UKRI Future Leaders Fellowship to L.T.B. (MR/V022067/1).
![](https://www.thieme-connect.de/media/synthesis/202215/lookinside/thumbnails/ss-2021-z0611-st_10-1055_s-0041-1737816-1.jpg)
Abstract
The synthetic versatility of thiophenols is offset by their air-sensitivity and foul odor. It is demonstrated that S-aryl isothiouronium salts can be used as precursors to thiyl radicals, extending the practical benefits of these air-stable, odorless salts from ionic to single electron manifolds. The isothiouronium salts are accessed via Ni-catalyzed cross-coupling of (hetero)aryl iodides and thiourea and are isolated as free-flowing solids following anion exchange. Judicious choice of a redox-innocent counteranion enables use of these convenient thiophenol surrogates in radical processes, as is exemplified by the synthesis of non-symmetrical diaryl thioethers via light-promoted S-arylation.
Key words
thiophenols - nickel catalysis - C–S cross-coupling - photochemistry - electron donor–acceptor complexes - thiyl radicals - diaryl sulfidesSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0041-1737816.
- Supporting Information
Publication History
Received: 13 October 2021
Accepted after revision: 10 January 2022
Article published online:
10 February 2022
© 2022. Thieme. All rights reserved
Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany
-
References
- 1 Ilardi EA, Vitaku E, Njardarson JT. J. Med. Chem. 2013; 57: 2832
- 2 Feng M, Tang B, Liang SH, Jiang X. Curr. Top. Med. Chem. 2016; 16: 1200
- 3 Lee C.-F, Liu Y.-C, Badsara SS. Chem. Asian J. 2014; 9: 706
- 4 Liu H, Jiang X. Chem. Asian J. 2013; 8: 2546
- 5 Kondo T, Mitsudo T. Chem. Rev. 2000; 100: 3205
- 6 Magné V, Ball LT. Chem. Eur. J. 2019; 25: 8903
- 7 Takagi K. Chem. Lett. 1985; 14: 1307
- 8 Dénès F, Pichowicz M, Povie G, Renaud P. Chem. Rev. 2014; 114: 2587
- 9 Liu B, Lim C.-H, Miyake GM. J. Am. Chem. Soc. 2017; 139: 13616
- 10 Liu B, Lim C.-H, Miyake GM. Synlett 2018; 29: 2449
- 11 Crisenza GE. M, Mazzarella D, Melchiorre P. J. Am. Chem. Soc. 2020; 142: 5461
- 12 It should be noted that relative to Miyake’s conditions, additional base was included to account for the initial deprotonation that enables thiophenol liberation from a neutral isothiourea. For mechanistic studies of isothiouronium decomposition, see: Pratt RF, Bruice TC. J. Am. Chem. Soc. 1972; 94: 2823
- 13 Hammerich O. In Organic Electrochemistry, 5th ed. CRC Press; Boca Raton: 2015: 1149
- 14 Rossi RA, Pierini AB, Peñéñory AB. Chem. Rev. 2003; 103: 71
- 15 Hernández-Muñoz LS, González FJ, González I, Goulart MO. F, de Abreu FC, Ribeiro AS, Ribeiro RT, Longo RL, Navarro M, Frontana C. Electrochim. Acta 2010; 55: 8325
- 16 Mandal A, Rissanen K, Mal P. CrystEngComm 2019; 21: 4401
- 17 ECHA substance infocard for NMP (accessed October 2021). https://echa.europa.eu/substance-information/-/substanceinfo/100.011.662