Subscribe to RSS
DOI: 10.1055/a-2798-1330
Dication Diselenides as Reservoirs of Open-Shell Catalysts in Covalent Radical Catalysis
Authors
Financial support from the Université Claude Bernard Lyon 1, ICBMS (UMR 5246), the CNRS and the Chinese Scholarship Council is gratefully acknowledged.
Supported by: Chinese Scolarship Council Supported by: ICBMS - UMR 5246

Abstract
Chalcogenyl radicals are powerful catalysts for covalent radical catalysis (CoRC), enabling the design of efficient radical cascades that transform simple substrates into valuable molecular architectures. Among them, selenium-centered radicals exhibit particularly attractive reactivity profiles, yet their broader exploitation has been hampered by the limited availability of suitable precursors. Herein, we report a novel family of dicationic diselenides that act as readily activatable reservoirs of selenyl radicals. Their physicochemical properties are elucidated, and their catalytic competence in CoRC is demonstrated, establishing dicationic diselenides as a new platform for selenium-based radical catalysis.
Publication History
Received: 31 December 2025
Accepted after revision: 27 January 2026
Accepted Manuscript online:
27 January 2026
Article published online:
05 February 2026
© 2026. Thieme. All rights reserved.
Georg Thieme Verlag KG
Oswald-Hesse-Straße 50, 70469 Stuttgart, Germany
-
References
- 1a Dénès F, Pichowicz M, Povie G, Renaud P. Chem Rev 2014; 114: 2587
- 1b Dong D-Q, Hao S-H, Yang D-S, Li L-X, Wang Z-L. Eur J Org Chem 2017; 6576
- 1c Wimmer A, König B. Beilstein J Org Chem 2018; 14: 54
- 1d Rafique J, Rampon DS, Azeredo JB, Coelho FL, Schneider PH, Braga AL. Chem Rec 2021; 21: 2739
- 1e Protti S, Fagnoni M. ACS Org Inorg Au 2022; 2: 455
- 1f Wang C, Zhang Y, Sun K, Yu T, Liu F, Wang X. Molecules 2023; 28: 1998
- 1g Kim K, Chae J. Synthesis 2025; 57: 1907
- 2a Xiao W, Wu J. ChemCatChem 2023; 15: e202300541
- 2b Archer G, Song K, Médebielle M, Merad J. ChemPhotoChem 2023; 7: e202300096
- 3a Subramanian H, Moorthy R, Sibi MP. Angew Chem Int Ed 2014; 53: 13660
- 3b Patehebieke Y. Beilstein J Org Chem 2020; 16: 1418
- 3c Lynch DM, Scanlan EM. Molecules 2020; 25: 3094
- 4 Feldman KS, Romanelli AL, Ruckle Jr RE, Miller RF. J Am Chem Soc 1988; 110: 3300
- 5a Singleton DA, Church KM. J Org Chem 1990; 55: 4780
- 5b Singleton DA, Church KM, Lucero MJ. Tetrahedron Lett 1990; 31: 5551
- 5c Singleton DA, Huval CC, Church KM, Priestley ES. Tetrahedron Lett 1991; 32: 5765
- 5d Huval CC, Singleton DA. J Org Chem 2020; 1994: 59
- 5e Jung ME, Rayle HL. J Org Chem 1997; 62: 4601
- 5f Hashimoto T, Takino K, Hato K, Maruoka K. Angew Chem Int Ed 2016; 55: 8081
- 5g Ryss JM, Turek AK, Miller SJ. Org Lett 2018; 20: 1621
- 5h Vyas H, Gangani AJ, Mini A. et al. Chem Eur J 2024; e202303175
- 6a Zhu X, Li P, Shi Q, Wang L. Green Chem 2016; 18: 637
- 6b Deng Y, Wei X-J, Wang H, Sun Y, Noël T, Wang X. Angew Chem Int Ed 2017; 56: 832
- 6c Zhao J, Yang F, Yu Z. et al. Chem Commun 2019; 55: 13008
- 7 Song K-L, Meyrelles R, Pilet G, Maryasin B, Médebielle M, Merad J. Angew Chem Int Ed 2025; 64: e202419751
- 8 Luo Y-R. Handbook of Bond Dissociation Energies in Organic Compounds. Boca Raton, FL: CRC Press; 2003
- 9 Zhiliaev K, Maryasin B, Kählig H, Gil-Sepulcre M, Mateos J. Angew Chem Int Ed 2025; 64: e202513534
- 10 Lin K, Luo-Wei C-R, Gao Y, Lan J, Zhu T. J Am Chem Soc 2025; 147: 31521
- 11 Maas G, Stang PJ. J Org Chem 1981; 46: 1606
- 12 Cernosek Z, Ruzicka A, Holubová J, Cernosková E. Main Group Met Chem 2007; 30: 231
- 13 General procedure for the synthesis of 6: To a 4 mL vial, equipped with a magnetic barrel was added 2 (0.5 mg, 0.6 μmol, 0.3 mol%). The vial was closed with a PTFE-septum screw cap and the atmosphere was exchanged for argon. Then, CH3CN (1.0 mL, previously degassed by bubbling argon for 10 min), VCP 4 (0.2 mmol, 1.0 equiv) and olefin 5 (0.4 mmol, 2.0 equiv) were added successively (VCP and olefin added before closing the vial if a solid). The vial was sealed with parafilm and irradiated with green LEDs (18 W Hepatochem®, 525 nm) for 16 h. The volatiles were then evaporated and the crude was purified by column chromatography.
- 14 6a was purified by column chromatography using petroleum ether/CH2Cl2 (20/80). Colourless oil (48 mg, 0.17 mmol, 85%), unseparable mixture of diastereomers: dr = 60:40. 1H NMR (300 MHz, Chloroform-d) δ 5.79–5.45 (m, 1H), 5.25–4.77 (m, 2H), 3.66–3.60 (m, 6H), 3.59–3.48 (m, 3H), 3.03–2.91 (m, 0.40H), 2.88–2.68 (m, 1H), 2.48–2.34 (m, 1.60H), 2.31–2.21 (m, 1H), 2.19–2.02 (m, 1H), 1.18 (s, 1.80H), 0.99 (s, 1.20H). 13C NMR (75 MHz, Chloroform-d) δ 176.4, 175.5, 173.3, 172.3, 171.9, 135.9, 135.7, 117.0, 116.7, 58.6, 57.7, 54.5, 52.92, 52.88, 52.82, 52.79, 52.6, 52.0, 51.9, 51.4, 49.6, 44.73, 44.71, 38.8, 37.4, 22.6, 18.8.
- 15 Kaga A, Yorimitsu H. In: Free Radicals: Fundamentals and Applications in Organic Synthesis 1. Fensterbank L. Ed. Thieme. Georg Thieme Verlag KG; Stuttgart: 2021