Generation of Thiyl Radicals from Air-Stable, Odorless Thiophenol Surrogates: Application to Visible-Light-Promoted C–S Cross-Coupling

Swan, Charlie; Maggi, Lorenzo; Park, Mahri; Taylor, Sophie; Shepherd, William; Ball, Liam T.

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.

Citation

Swan, C., Maggi, L., Park, M., Taylor, S., Shepherd, W., & Ball, L. T. (2022). Generation of Thiyl Radicals from Air-Stable, Odorless Thiophenol Surrogates: Application to Visible-Light-Promoted C–S Cross-Coupling. SYNTHESIS, 15(54), 3399-3408. https://doi.org/10.1055/s-0041-1737816

• Journal Article Type: Article
• Acceptance Date: Jan 10, 2022
• Online Publication Date: Feb 10, 2022
• Publication Date: 2022-08
• Deposit Date: Feb 17, 2022
• Publicly Available Date: Feb 11, 2023
• Journal: Synthesis
• Print ISSN: 0039-7881
• Electronic ISSN: 1437-210X
• Publisher: Georg Thieme Verlag KG
• Peer Reviewed: Peer Reviewed
• Volume: 15
• Issue: 54
• Pages: 3399-3408
• DOI: https://doi.org/10.1055/s-0041-1737816
• Keywords: Organic Chemistry; Catalysis
• Public URL: https://nottingham-repository.worktribe.com/output/7418368
• Publisher URL: https://www.thieme-connect.de/products/ejournals/abstract/10.1055/s-0041-1737816