Inexpensive and bench stable diarylmethylium tetrafluoroborates as organocatalysts in the light mediated hydrosulfonylation of unactivated alkenes

• Published in: Chemical science (Cambridge) Vol. 14; no. 1; pp. 2721 - 2734
• Main Authors: Renzi, Polyssena, Azzi, Emanuele, Ascensio, Sylvain, Parisotto, Stefano, Sordello, Fabrizio, Pellegrino, Francesco, Ghigo, Giovanni, Deagostino, Annamaria
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 08-03-2023; The Royal Society of Chemistry
• Subjects: Alkenes; Catalysts; Charge transfer; Chemistry; Electron transfer; Radicals; Reforming
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/d3sc00182b

In this paper, we present the synthetic potential of diarylmethylium tetrafluoroborates as catalysts for the visible light promoted hydrosulfonylation of unactivated alkenes. For the first time, these salts, which are bench stable and easily preparable on a multi-gram scale, were employed as organocatalysts. Interestingly, a catalyst loading of only 1 mol% allowed sulfone products to be efficiently obtained from good-to-excellent yields with high functional-group tolerance and scalability up to 15 mmol of alkene. The mechanistic study, both experimental and computational, presented here, revealed an alternative mechanism for the formation of the key sulfonyl radical. Indeed, the photoactive species was proved not to be the diarylcarbenium salt itself, but two intermediates, a stable S-C adduct and an ion couple, that were formed after its interaction with sodium benzenesulfinate. Upon absorbing light, the ion couple could reach an excited state with a charge-transfer character which gave the fundamental sulfonyl radical. A PCET (proton-coupled electron transfer) closes the catalytic cycle reforming the diarylcarbenium salt.
Can a cheap and bench stable salt catalyse the hydrosulfonylation of unactivated alkenes? Yes it does! Just mix a diarylmethylium tetrafluoroborate salt with a sulfinate salt, wait for the formation of the adduct and turn purple light on it.