Abstract
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.
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Translated from Zhurnal Strukturnoi Khimii, Vol. 48, Supplement, pp. S101–S106, 2007.
Original Russian Text Copyright © 2007 by E. Yu. Larionova, N. M. Vitkovskaya, V. B. Kobychev, N. V. Shevchenko, and B. A. Trofimov
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Larionova, E.Y., Vitkovskaya, N.M., Kobychev, V.B. et al. Ab initio quantum-chemical study of the reaction mechanisms of acetylene in superbasic media. Noncatalytic vinylation of methanol. J Struct Chem 48 (Suppl 1), S94–S99 (2007). https://doi.org/10.1007/s10947-007-0152-3
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DOI: https://doi.org/10.1007/s10947-007-0152-3