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Deoxygenation of Phosphine Oxides by PIII/PV═O Redox Catalysis via Successive Isodesmic Reactions
- Source :
- Journal of the American Chemical Society; July 2023, Vol. 145 Issue: 28 p15589-15599, 11p
- Publication Year :
- 2023
-
Abstract
- Deoxygenation of phosphine oxides is of great significance to synthesis of phosphorus ligands and relevant catalysts, as well as to the sustainability of phosphorus chemistry. However, the thermodynamic inertness of P═O bonds poses a severe challenge to their reduction. Previous approaches in this regard rely primarily on a type of P═O bond activation with either Lewis/Brønsted acids or stoichiometric halogenating reagents under harsh conditions. Here, we wish to report a novel catalytic strategy for facile and efficient deoxygenation of phosphine oxides via successive isodesmic reactions, whose thermodynamic driving force for breaking the strong P═O bond was compensated by a synchronous formation of another P═O bond. The reaction was enabled by PIII/P═O redox sequences with the cyclic organophosphorus catalyst and terminal reductant PhSiH3. This catalytic reaction avoids the use of the stoichiometric activator as in other cases and features a broad substrate scope, excellent reactivities, and mild reaction conditions. Preliminary thermodynamic and mechanistic investigations disclosed a dual synergistic role of the catalyst.
Details
- Language :
- English
- ISSN :
- 00027863 and 15205126
- Volume :
- 145
- Issue :
- 28
- Database :
- Supplemental Index
- Journal :
- Journal of the American Chemical Society
- Publication Type :
- Periodical
- Accession number :
- ejs63470063
- Full Text :
- https://doi.org/10.1021/jacs.3c05270