Nguyen Thi Hong Van, Chelli Saloua, Mallet-Ladeira Sonia, Breugst Martin, Lakhdar Sami
CNRS, Université Paul Sabatier, Laboratoire Hetérochimie Fondamentale et Appliquée (LHFA, UMR5069) 118 Route de Narbonne 31062 Cedex 09 Toulouse France
Institut de Chimie de Toulouse (FR 2599) 118 Route de Narbonne 31062 Cedex 09 Toulouse France.
Chem Sci. 2024 Aug 8;15(35):14406-14. doi: 10.1039/d4sc03518f.
The reactivity of sodium phosphaethynolate Na(OCP) towards various Mayr's reference electrophiles was investigated using conventional UV-visible and laser-flash photolysis techniques. The kinetic data, along with density functional theory (DFT) calculations, enabled the first experimental quantification of the phosphorus nucleophilicity of [OCP]. Product studies of these reactions demonstrate the formation of secondary as well as tertiary phosphines. The mechanism of this unprecedented phosphorus-atom transfer reaction is thoroughly discussed, with key intermediates successfully isolated and characterized. Importantly, some bulky secondary phosphine oxides synthesized using this approach, have demonstrated high efficiency as ligands in the Suzuki coupling reaction.
采用传统紫外可见光谱和激光闪光光解技术研究了磷乙炔醇钠Na(OCP)与各种迈尔参考亲电试剂的反应活性。动力学数据以及密度泛函理论(DFT)计算,实现了对[OCP]磷亲核性的首次实验量化。这些反应的产物研究表明形成了仲膦和叔膦。对这种前所未有的磷原子转移反应的机理进行了深入讨论,成功分离并表征了关键中间体。重要的是,用这种方法合成的一些大体积仲膦氧化物在铃木偶联反应中作为配体表现出了高效率。