过渡金属催化的惰性化学键的选择性氧化磷酰化反应研究

Phosphates and derivatives are an important class of molecules because of their broad application in medicinal chemistry, material chemistry and catalytic chemistry. However, efficient synthetic methods for phosphates remain limited due to several questions such as tedious steps，low reactivity and poor selectivity. This project aims to develop a novel transition-metal-catalyzed regioselective oxidative phosphorylating of unactivated chemical bonds, such as α、β、γ-C(sp3)-H and C(sp3)-C. This project represents an efficient strategy and method for the synthesis of alkyl phosphates from readily available materials. Through exploring various factors to influence the reaction and using 31PNMR，EPR and X-ray single crystal diffraction, the reaction kinetics and reaction mechanism will be investigated, and the catalytic model on the basis of metal-catalyzed oxidative phosphorylating will be preliminarily established, providing theory foundation on oxidative phosphorylating of more inert chemical bonds. Compared with traditional methods, this protocol has many good advantages: 1) step-economical avoiding prefunctionalized processes; 2) atom-economical with only two hydrogen atoms lost; 3) environmentally friendly with H2O and CO2 as the only waste.

磷酸酯及其衍生物是一类非常重要的化合物，已经广泛应用在药物化学、材料化学和催化化学等领域中。然而目前合成方法却十分有限，普遍存在着步骤冗长、反应活性低和选择性差等问题。本项目旨在发展新型过渡金属催化的区域选择性的α、β、γ-C(sp3)-H氧化磷酰化反应及碳碳键的氧化磷酰化反应，使其成为一种利用简单原料合成烷基磷酸酯化合物的有效手段。通过探索影响反应的各种因素，并利用31PNMR、X射线单晶衍射和EPR等方法研究反应动力学和反应机理，建立金属催化氧化磷酰化的催化模型，为更多的惰性化学键的氧化磷酰化反应提供理论基础。与传统方法相比，底物不需要预先合成，大大缩短了合成步骤；反应中仅失去两个氢原子，原子经济性高；副产物为H2O、CO2等, 环境友好。

本项目主要发展了过渡金属催化的惰性化学键比如碳氢、硫氢和碳碳键的选择性氧化磷酰化、烷基化、氨基化、硫氰化、硒氰化反应，高效构建了一系列碳杂键。通过探索影响反应的各种因素，并利用核磁共振、同位素实验和电子顺磁共振等方法研究了反应动力学和反应机理，建立了金属催化氧化官能化的催化模型，为更多的惰性化学键的氧化官能化反应提供了理论基础。与传统方法相比，底物不需要预先合成，大大缩短了合成步骤；反应中仅失去两个氢原子，原子经济性高；副产物为H2O、CO2等, 环境友好。