Copper-Phosphido Catalysis: Enantioselective Addition of Phosphines to Cyclopropenes.
Copper-Phosphido Catalysis: Enantioselective Addition of Phosphines to Cyclopropenes.
复制标题
铜-磷基催化：膦对环丙烯的对映选择性加成。
DOI：
10.1002/anie.202306511
复制
发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Nie,Shaozhen
中科院分区：
文献类型：
--
作者：
Daniels,BrianS;Hou,Xintong;Corio,StephanieA;Weissman,LindseyM;Dong,VyM;Hirschi,JenniferS;Nie,Shaozhen
我们描述了一种铜催化剂，可促进膦在环境温度下加成到环丙烯上。现在可以以高产率和对映选择性获得一系列具有不同空间和电子特性的环丙基膦。磷立构中心的富集也通过动态动力学不对称转化（DyKAT）过程得到证明。实验和理论相结合的机理研究支持了将 CuI-磷基插入碳-碳双键的基本步骤。密度泛函理论计算揭示了迁移插入是速率和立体决定步骤，随后是异步原脱金属化。
We describe a copper catalyst that promotes the addition of phosphines to cyclopropenes at ambient temperature. A range of cyclopropylphosphines bearing different steric and electronic properties can now be accessed in high yields and enantioselectivities. Enrichment of phosphorus stereocenters is also demonstrated via a Dynamic Kinetic Asymmetric Transformation (DyKAT) process. A combined experimental and theoretical mechanistic study supports an elementary step featuring insertion of a CuI‐phosphido into a carbon‐carbon double bond. Density functional theory calculations reveal migratory insertion as the rate‐ and stereo‐determining step, followed by asyn‐protodemetalation.