Inexpensive and bench stable diarylmethylium tetrafluoroborates as organocatalysts in the light mediated hydrosulfonylation of unactivated alkenes
Articolo
Data di Pubblicazione:
2023
Abstract:
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.
Tipologia CRIS:
03A-Articolo su Rivista
Elenco autori:
Renzi, Polyssena; Azzi, Emanuele; Ascensio, Sylvain; Parisotto, Stefano; Sordello, Fabrizio; Pellegrino, Francesco; Ghigo, Giovanni; Deagostino, Annamaria
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