Ab initio quantum-chemical study of the reaction mechanisms of acetylene in superbasic media. Noncatalytic vinylation of methanol

作者：Larionova E Yu^*; Vitkovskaya N M; Kobychev V B; Shevchenko N V; Trofimov B A

来源：Journal of Structural Chemistry, 2007, 48: S94-S99.

DOI：10.1007/s10947-007-0152-3

• vinyl ethers
• vinylation
• methoxide ion
• mechanism
• quantum-chemical calculations

The reaction profile of noncatalytic vinylation of methanol with acetylene was Studied by ab initio quantum-chemical calculations for the gas phase and by calculations using a combined model that took into account the solvent (DMSO) effect. The reaction Occurs via the formation of a prereaction complex of the methoxide ion with acetylene; at this stage, the acetylene molecule is already activated with respect to the proton. The observed stereospecific trans-addition in methanol vinylation in the gas phase and solution is provided by the lower activation barrier corresponding to the E structure of the acetylene molecule in the transition state and barrier-free protonation of the carbanion intermediate.

• 出版日期2007-12