anti-Markovnikov addition of tellurium tetrachloride to trimethyl ethynyl silane

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• 作者：S.V. Amosova ; A.V. Martynov ; V.A. Shagun ; M.V. Musalov ; L.I. Larina ; L.B. Krivdin ; L.V. Zhilitskaya ; M.G. Voronkov
• 关键词：anti-Markovnikov addition ; Ethynyl silane ; Tellurium tetrachloride ; Multinuclear NMR spectroscopy ; Quantum-chemical calculations
• 刊名：Journal of Organometallic Chemistry
• 出版年：2008
• 期刊代码：64_0022328x
• 类别：ch
• 出版时间：15 July 2008
• 卷：693
• 期：15
• 页码：2509-2513
• 文件大小：385 K

摘要

An investigation of the TeCl₄ interaction with trimethyl ethynyl silane 1 in CHCl₃ has shown that anti-Markovnikov adduct [Z-1-(trimethylsilyl)-2-chlorovinyl]tellurium trichloride is formed as the only product. In time, it is hydrolyzed to give [Z-1-(trimethylsilyl)-2-chlorovinyl]tellurium (hydroxy) dichloride which, in turn, is dehydrated to afford bis[(2-chloro-1-trimethyl-silylvinyl)dichlorotellurium]oxide. These data revealed that the reaction studied was the first example of anti-Markovnikov syn-addition of TeCl₄ to terminal acetylenes. A computed simulation of the TeCl₄ interaction with ethynyl silane 1 in a gas state using PES method did not reveal dominating orientation of the addition but showed the conditions at which anti-Markovnikov addition can occur and which were probably met in carrying out the reaction in CHCl₃.