Terminal Alkyne Coupling Reactions through a Ring: Mechanistic Insights and Regiochemical Switching,Angewandte Chemie International Edition

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Terminal Alkyne Coupling Reactions through a Ring: Mechanistic Insights and Regiochemical Switching
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2018-08-20 , DOI: 10.1002/anie.201807028
Caroline M Storey ₁ , Matthew R Gyton ₁ , Rhiann E Andrew ₁ , Adrian B Chaplin ₁

Affiliation

The mechanism and selectivity of terminal alkyne coupling reactions promoted by rhodium(I) complexes of NHC‐based CNC pincer ligands have been investigated. Synthetic and kinetic experiments support E‐ and gem‐enyne formation through a common reaction sequence involving hydrometallation and rate‐determining C−C bond reductive elimination. The latter is significantly affected by the ligand topology: Employment of a macrocyclic variant enforced exclusive head‐to‐head coupling, contrasting the high selectivity for head‐to‐tail coupling observed for the corresponding acyclic pincer ligand.

中文翻译：

通过环的末端炔偶联反应：机理见解和区域化学转换

研究了 NHC 基 CNC 钳配体的铑 (I) 配合物促进的末端炔烃偶联反应的机理和选择性。合成和动力学实验通过涉及加氢金属化和速率决定的 C−C 键还原消除的常见反应序列支持 E- 和偕烯炔的形成。后者受配体拓扑结构的显着影响：大环变体的使用强制了排他性的头对头耦合，与相应的无环钳配体观察到的头对尾耦合的高选择性形成鲜明对比。

更新日期：2018-08-20

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