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DFT Study of the Nucleophilic Addition of Water to Ketenes
Author(s) -
RodríguezOtero Jesús,
HermidaRamón Jose M.,
CabaleiroLago Enrique M.
Publication year - 2007
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200600932
Subject(s) - chemistry , nucleophile , density functional theory , transition state , computational chemistry , reaction mechanism , gas phase , nucleophilic addition , solvent , nucleophilic substitution , concerted reaction , solvent effects , organic chemistry , catalysis
The geometries of the different stationary points of reactants, products, and transition states of the nucleophilic addition of water to cyanoketene and methylcarboxyketene have been identified by optimizing every degree of freedom by density functional theory at the B3LYP/6‐31++G** level of theory. The computational results for methylcarboxyketene in both the gas and solvated phase agree with the explanation based on experimental data, according to which the nucleophilic addition of water or alcohols to ketenes obtained from malonates (in our case represented by methylcarboxyketene) occurs by a concerted pseudopericyclic mechanism. The results of the calculations also agree with the experimental data for addition to cyanoketene. This reaction occurs through a zwitterionic intermediate, but in contrast to the previous reaction the solvent is essential for the process to occur.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)