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A theoretical study of methanol vinylation reaction mechanism
Author(s) -
Vitkovskaya Nadezhda M.,
Larionova Elena Yu.,
Kobychev Vladimir B.,
Kaempf Natalia V.,
Trofimov Boris A.
Publication year - 2008
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.21639
Subject(s) - chemistry , methanol , solvation , dimethyl sulfoxide , alkali metal , methoxide , nucleophile , solvent , photochemistry , computational chemistry , medicinal chemistry , base (topology) , catalysis , organic chemistry , mathematical analysis , mathematics
The mechanism of base‐catalyzed nucleophilic addition of methanol to acetylene triple bond (vinylation) in dimethyl sulfoxide (DMSO) and methanol solution was studied using the MP2/6‐311++G**//B3LYP/6‐31G* calculations with solvent effects included via continuum model. The proton abstraction from methanol by nondissociated alkali in DMSO surrounding media to form alkali metal methoxides CH 3 OM ( M = Li, Na, K) was found to occur with a negligible activation barrier. The reasons for facilitation of base‐catalyzed alcohol vinylation in the DMSO medium are discussed in the light of both poor solvation of methoxide ion and a specific coordination of reactants by nondissociated alkali in the MOH/DMSO mixtures. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008