铜催化酸循环添加中的X连接体的Janus面
Liqun Jin1, Erik A Romero1, Mohand Melaimi1
1UCSD-CNRS Joint Research Laboratory (UMI 3555), Department of Chemistry and Biochemistry, University of California, San Diego , La Jolla, California 92093-0358, United States.
Journal of the American Chemical Society
|November 28, 2015
概括
铜催化酸循环添加 (CuAAC) 中的离子 (X) 显著影响反应动力学. 乙酸提供平衡,优化有效催化的主要步骤.
科学领域:
- 催化剂
- 有机化学
- 反应机制
背景情况:
- 铜催化酸循环添加 (CuAAC) 是各种化学领域的关键反应.
- 对于优化CuAAC效率至关重要的是了解连接体和对子的作用.
研究的目的:
- 阐明阴离子 (X) 对CuAAC催化循环中的单个步骤的动力学的影响.
- 为提高催化性能确定最佳的联体-离子组合.
主要方法:
- 使用复合铜与循环 (基) 氨基) 碳素 (CAAC) 配体和各种离子 (OTf,Cl,OAc,OPh,OtBu) 进行了固体测量反应.
- 分析了催化循环步骤的动态概况.
主要成果:
- 基本配体加速金属化,但阻碍了二氧化铜乙的形成.
- 非核性配体有利于双铜乙化形成,但金属化速度较慢.
- 乙酸 (OAc) 在化和双铜乙化形成之间表现出有利的平衡.
- 在原始脱金属化阶段,乙酸的效率非常高.
结论:
- 在CuAAC中的选择显著影响了关键催化步骤的速度.
- 循环 () 氨基) 碳 (CAAC) 铜复合体与酸盐离子代表了高效CuAAC反应的有希望的系统.
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