anti-Markovnikov addition of tellurium tetrachloride to trimethyl ethynyl silane

作者：Amosova S V^*; Martynov A V; Shagun V A; Musalov M V; Larina L I; Krivdin L B; Zhilitskaya L V; Voronkov M G

来源：Journal of Organometallic Chemistry, 2008, 693(15): 2509-2513.

DOI：10.1016/j.jorganchem.2008.04.041

• anti-Markovnikov addition
• ethynyl silane
• tellurium tetrachloride
• multinuclear NMR spectroscopy
• quantum-chemical calculations

An investigation of the TeCl(4) interaction with trimethyl ethynyl silane 1 in CHCl(3) 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 TeCl(4) to terminal acetylenes. A computed simulation of the TeCl(4) 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 CHCl(3).

• 出版日期2008-7-15