通过电化学诱导的分子内途径实现醛的直接三氟甲基硅基化和氰基硅基化反应。
The direct trifluoromethylsilylation and cyanosilylation of aldehydes via an electrochemically induced intramolecular pathway.
作者信息
Yang Hui, Shen Yongli, Xiao Zihui, Liu Caiyan, Yuan Kedong, Ding Yi
机构信息
Tianjin Key Laboratory of Advanced Functional Porous Materials, Institute for New Energy Materials & Low-Carbon Technologies, School of Materials Science and Engineering, Tianjin University of Technology, Tianjin 300384, P. R. China.
出版信息
Chem Commun (Camb). 2020 Feb 25;56(16):2435-2438. doi: 10.1039/c9cc08975f.
The initiator-free electrochemical trifluoromethylsilylation and cyanosilylation of aldehydes were developed in an undivided cell. A DFT study reveals that the direct cathodic activation of trimethylsilyl reagents significantly released the congestion around the 'Si' atom, allowing the Si-O bond affinity to form concerted anion intermediates with aldehydes. Thus, intramolecular -CF3 and -CN migration make the reactions much easier to carry out without initiators.
醛的无引发剂电化学三氟甲基硅基化反应和氰基硅基化反应是在无隔膜电解池中进行的。一项密度泛函理论（DFT）研究表明，三甲基硅基试剂的直接阴极活化显著缓解了“Si”原子周围的拥挤状况，使得Si-O键亲和力能够与醛形成协同阴离子中间体。因此，分子内的-CF3和-CN迁移使得这些反应在没有引发剂的情况下更容易进行。
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