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DFT study on the role of methanol solvent in Morita–Baylis–Hillman reaction
Author(s) -
Fan JianFen,
Yang ChunHong,
He LiangJun
Publication year - 2009
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.21945
Subject(s) - chemistry , solvent , methanol , transition state , molecule , supramolecular chemistry , computational chemistry , formaldehyde , solvent effects , transition state theory , catalysis , photochemistry , organic chemistry , reaction rate constant , kinetics , physics , quantum mechanics
B3LYP/6‐311++G** calculations have been carried out to study the role of methanol solvent in the trimethylamine‐catalyzed Morita‐Baylis‐Hillman reaction between acraldehyde and formaldehyde with CPCM solvent method and supramolecular model with one explicit CH 3 OH solvent molecule, respectively. The optimized geometries and energies of the reactant complexes, intermediates, transition states, and products of the two reaction channels (corresponding to the scenarios of syn ‐ and anti ‐acraldehyde, respectively) were obtained, and the relative energy profiles were completed. The results reveal that CH 3 OH solvent molecules can stabilize the zwitterionic intermediates and largely reduce the barrier of H transfer process by taking part in the formation of the transition state in this process. CC bond formation step is the rate‐determining step of the whole reaction cycle. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009