Eloïse Bréger, Jade Dussart-Gautheret, Rachid Taakili, Fabien Fontaine-Vive, Christopher C Cummins, Rachid Benhida
{"title":"A Remarkable Catalyst-Free Photochemical Alkene Hydrophosphination with Bis(trimethylsilyl)phosphonite.","authors":"Eloïse Bréger, Jade Dussart-Gautheret, Rachid Taakili, Fabien Fontaine-Vive, Christopher C Cummins, Rachid Benhida","doi":"10.1021/jacsau.5c00444","DOIUrl":null,"url":null,"abstract":"<p><p>This publication delves into a comprehensive exploration of a new synthetic route to functionalized phosphorus-derived compounds. Bis-(trimethylsilyl)-phosphonite HP-(OSiMe<sub>3</sub>)<sub>2</sub>, prepared in a high yield from H<sub>3</sub>PO<sub>2</sub>, was found to be an excellent reagent for hydrophosphination of activated, unactivated, and amino acid-derived olefins under UV irradiation and catalyst-, solvent- and glovebox-free conditions. The resulting phosphorus trivalent compounds have been subjected to postfunctionalization, leading to the formation of <i>H</i>-phosphinate, phosphonate, and thiophosphonate end products in good to excellent yields. With a combination of experimental and theoretical calculations, the mechanism for this hydrophosphination reaction has been investigated, revealing a radical process.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 6","pages":"2861-2870"},"PeriodicalIF":8.5000,"publicationDate":"2025-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12188422/pdf/","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"JACS Au","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1021/jacsau.5c00444","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2025/6/23 0:00:00","PubModel":"eCollection","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
This publication delves into a comprehensive exploration of a new synthetic route to functionalized phosphorus-derived compounds. Bis-(trimethylsilyl)-phosphonite HP-(OSiMe3)2, prepared in a high yield from H3PO2, was found to be an excellent reagent for hydrophosphination of activated, unactivated, and amino acid-derived olefins under UV irradiation and catalyst-, solvent- and glovebox-free conditions. The resulting phosphorus trivalent compounds have been subjected to postfunctionalization, leading to the formation of H-phosphinate, phosphonate, and thiophosphonate end products in good to excellent yields. With a combination of experimental and theoretical calculations, the mechanism for this hydrophosphination reaction has been investigated, revealing a radical process.