Understanding the mechanism and reactivity of Pd-catalyzed C-P bond metathesis of aryl phosphines: a computational study.,Organic & Biomolecular Chemistry

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Understanding the mechanism and reactivity of Pd-catalyzed C-P bond metathesis of aryl phosphines: a computational study.
Organic & Biomolecular Chemistry ( IF 2.9 ) Pub Date : 2020-06-26 , DOI: 10.1039/d0ob00719f
Shao-Qi Wu ₁ , Shuo-Qing Zhang ₁ , Xin Hong ₂

Affiliation

Transition metal-catalyzed single bond metathesis has recently emerged as a useful strategy for functional group transfer. In this work, we explored the mechanism and reactivity profile of Pd/PhI-cocatalyzed C–P bond metathesis between aryl phosphines using density functional theory (DFT) calculations. The overall single bond metathesis involves two Pd(II)-catalyzed C–P reductive eliminations and two Pd(0)-catalyzed C–P oxidative additions, which allows the reversible C–P bond cleavage and formation of the phosphonium cation. Distortion/interaction analysis indicates that the facile C–P bond cleavage and formation of the phosphonium cation are due to the involvement of coordinating aryl phosphine in the process. In addition, the substituent effects on the reaction kinetics and thermodynamics of metathesis were computed, which provides helpful mechanistic information for the design of related single bond metathesis reactions.

中文翻译：

了解Pd催化芳基膦的CP键复分解的机理和反应性：一项计算研究。

过渡金属催化的单键复分解最近已成为一种有用的官能团转移策略。在这项工作中，我们使用密度泛函理论（DFT）计算探索了芳基膦之间Pd / PhI共同催化的C–P键复分解的机理和反应活性。整体单键复分解涉及两个Pd（II）催化的C–P还原消除和两个Pd（0）催化的C–P氧化添加，这允许可逆的C–P键裂解和formation阳离子的形成。畸变/相互作用分析表明，容易进行的C-P键断裂和阳离子的形成是由于在此过程中涉及了配位芳基膦。此外，计算了取代基对复分解反应动力学和热力学的影响，为相关单键复分解反应的设计提供了有用的机理信息。

更新日期：2020-07-22

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