为了证明异氰化物在催化CH键官能化反应中的实用性,开发了2-卤代双芳基与异氰化物的钯催化的环偶联反应。该反应通过在2-卤代联芳基的2'-位上的CH键断裂,提供了一系列芴酮亚胺衍生物。2,6-二取代的苯基异氰化物的使用对于进行该催化环偶联反应至关重要。该反应适用于杂环和乙烯基底物,从而允许构建广泛的环系统。观察到的大的动力学同位素效应(k H / k D = 5.3)表明,CH键的活化是该催化作用中的周转限制步骤。
Regioselectivity of photochemical annulations of chromium carbene complexes
作者:Craig A. Merlic、W.Michael Roberts
DOI:10.1016/s0040-4039(00)60130-2
日期:1993.11
The regioselectivity of photochemical benzannulation reactions of chromium biarylcarbene complexes is reported. Excellent selectivity is observed in furyl- and naphthyl-substituted substrates. Interesting ortho verses para selectivity is found in meta substituted (biphenyl)carbene substrates.
Expeditious Synthesis of Tetrasubstituted Helical Alkenes by a Cascade of Palladium-Catalyzed CH Activations
作者:Hongqiang Liu、Mohamed El-Salfiti、Mark Lautens
DOI:10.1002/anie.201204226
日期:2012.9.24
Twisted molecules: A modular approach for the synthesis of tetrasubstitutedhelicalalkenes by a palladium‐catalyzed norbornene‐mediated domino reaction is presented. This intermolecular domino process allows the formation of three CC bonds in one operation through a CH activation/carbopalladation/CH activation sequence.
扭曲分子:提出了一种通过钯催化的降冰片烯介导的多米诺反应合成四取代螺旋烯烃的模块化方法。此分子间多米诺过程允许的三个C的形成在一个操作中C键通过C ħ激活/ carbopalladation / C ħ激活序列。