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

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 organoc...

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Autores principales: Renzi, Polyssena, Azzi, Emanuele, Ascensio, Sylvain, Parisotto, Stefano, Sordello, Fabrizio, Pellegrino, Francesco, Ghigo, Giovanni, Deagostino, Annamaria
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9993860/
https://www.ncbi.nlm.nih.gov/pubmed/36908942
http://dx.doi.org/10.1039/d3sc00182b
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author Renzi, Polyssena
Azzi, Emanuele
Ascensio, Sylvain
Parisotto, Stefano
Sordello, Fabrizio
Pellegrino, Francesco
Ghigo, Giovanni
Deagostino, Annamaria
author_facet Renzi, Polyssena
Azzi, Emanuele
Ascensio, Sylvain
Parisotto, Stefano
Sordello, Fabrizio
Pellegrino, Francesco
Ghigo, Giovanni
Deagostino, Annamaria
author_sort Renzi, Polyssena
collection PubMed
description 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.
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spelling pubmed-99938602023-03-09 Inexpensive and bench stable diarylmethylium tetrafluoroborates as organocatalysts in the light mediated hydrosulfonylation of unactivated alkenes Renzi, Polyssena Azzi, Emanuele Ascensio, Sylvain Parisotto, Stefano Sordello, Fabrizio Pellegrino, Francesco Ghigo, Giovanni Deagostino, Annamaria Chem Sci Chemistry 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. The Royal Society of Chemistry 2023-02-10 /pmc/articles/PMC9993860/ /pubmed/36908942 http://dx.doi.org/10.1039/d3sc00182b Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Renzi, Polyssena
Azzi, Emanuele
Ascensio, Sylvain
Parisotto, Stefano
Sordello, Fabrizio
Pellegrino, Francesco
Ghigo, Giovanni
Deagostino, Annamaria
Inexpensive and bench stable diarylmethylium tetrafluoroborates as organocatalysts in the light mediated hydrosulfonylation of unactivated alkenes
title Inexpensive and bench stable diarylmethylium tetrafluoroborates as organocatalysts in the light mediated hydrosulfonylation of unactivated alkenes
title_full Inexpensive and bench stable diarylmethylium tetrafluoroborates as organocatalysts in the light mediated hydrosulfonylation of unactivated alkenes
title_fullStr Inexpensive and bench stable diarylmethylium tetrafluoroborates as organocatalysts in the light mediated hydrosulfonylation of unactivated alkenes
title_full_unstemmed Inexpensive and bench stable diarylmethylium tetrafluoroborates as organocatalysts in the light mediated hydrosulfonylation of unactivated alkenes
title_short Inexpensive and bench stable diarylmethylium tetrafluoroborates as organocatalysts in the light mediated hydrosulfonylation of unactivated alkenes
title_sort inexpensive and bench stable diarylmethylium tetrafluoroborates as organocatalysts in the light mediated hydrosulfonylation of unactivated alkenes
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9993860/
https://www.ncbi.nlm.nih.gov/pubmed/36908942
http://dx.doi.org/10.1039/d3sc00182b
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