A Remarkable Catalyst-Free Photochemical Alkene Hydrophosphination with Bis(trimethylsilyl)phosphonite
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.
Authors
- Fabien Fontaine‐Vive (ORCID: https://orcid.org/0000-0002-7679-5490)
- Rachid Taakili (ORCID: https://orcid.org/0000-0001-9084-0625)
- Christopher C. Cummins (ORCID: https://orcid.org/0000-0003-2568-3269)
- Jade Dussart‐Gautheret (ORCID: https://orcid.org/0000-0001-7434-3741)
- Rachid Benhida (ORCID: https://orcid.org/0000-0003-3419-5697)
- Eloïse Bréger
Institutions
- Université Côte d'Azur (FR)
- Institut de Chimie de Nice (FR)
- Laboratoire de Chimie de Coordination (FR)
- The Polytechnic University of Japan (JP)
- Observatoire de la Côte d’Azur (FR)
- Université Mohammed VI Polytechnique (MA)
- Massachusetts Institute of Technology (US)
Publication Details
- Journal
- JACS Au
- Published
- 2025-06-03
- DOI
- https://doi.org/10.1021/jacsau.5c00444
- Citations
- 2
- Primary Topic
- Organophosphorus compounds synthesis
- Type
- article
- Field-Weighted Citation Impact
- 1.87
Funders
- Université Mohammed VI Polytechnique