caa a22 4500 463239822 CHVBK 20180405153309.0 cr unu---uuuuu 170326e20070101xx s 000 0 eng 10.1007/s10947-007-0152-3 doi (NATIONALLICENCE)springer-10.1007/s10947-007-0152-3 Ab initio quantum-chemical study of the reaction mechanisms of acetylene in superbasic media. Noncatalytic vinylation of methanol [Elektronische Daten] [E. Larionova, N. Vitkovskaya, V. Kobychev, N. Shevchenko, B. Trofimov] 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. Springer Science+Business Media, Inc., 2007 vinyl ethers nationallicence vinylation nationallicence methoxide ion nationallicence mechanism nationallicence quantum-chemical calculations nationallicence Larionova E. Irkutsk State University, Irkutsk aut Vitkovskaya N. Irkutsk State University, Irkutsk aut Kobychev V. Irkutsk State University, Irkutsk aut Shevchenko N. Irkutsk State University, Irkutsk aut Trofimov B. A. E. Favorskii Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk aut Journal of Structural Chemistry Springer US 48(2007-01-01), S94-S99 0022-4766 48<S94 2007 48 10947 https://doi.org/10.1007/s10947-007-0152-3 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s10947-007-0152-3 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Larionova E. Irkutsk State University, Irkutsk aut NATIONALLICENCE 700 1- Vitkovskaya N. Irkutsk State University, Irkutsk aut NATIONALLICENCE 700 1- Kobychev V. Irkutsk State University, Irkutsk aut NATIONALLICENCE 700 1- Shevchenko N. Irkutsk State University, Irkutsk aut NATIONALLICENCE 700 1- Trofimov B. A. E. Favorskii Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk aut NATIONALLICENCE 773 0- Journal of Structural Chemistry Springer US 48(2007-01-01), S94-S99 0022-4766 48<S94 2007 48 10947 Metadata rights reserved Springer special CC-BY-NC licence nationallicence SWISSBIB 453116736 BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer