PMID: 9192609Jun 24, 1997Paper

Nonenzymatic and enzymatic hydrolysis of alkyl halides: a theoretical study of the SN2 reactions of acetate and hydroxide ions with alkyl chlorides

Proceedings of the National Academy of Sciences of the United States of America
A H MaulitzThomas C Bruice

Abstract

The SN2 displacements of chloride ion from CH3Cl, C2H5Cl, and C2H4Cl2 by acetate and hydroxide ions have been investigated, using ab initio molecular orbital theory at the HF/6-31+G(d), MP2/6-31+G(d), and MP4/6-31+G(d) levels of theory. The central barriers (calculated from the initial ion-molecule complex) of the reactions, the differences of the overall reaction energies, and the geometries of the transition states are compared. Essential stereochemical changes before and after the displacement reactions are described for selected cases. The gas phase reactions of hydroxide with CH3Cl, C2H5Cl, and C2H4Cl2 have no overall barrier, but there is a small overall barrier for the reactions of acetate with CH3Cl, C2H5Cl, and C2H4Cl2. A self-consistent reaction field solvation model was used to examine the SN2 reactions between methyl chloride and hydroxide ion and between 1,2-dichloroethane and acetate in solution. As expected, the reactions in polar solvent have a large barrier. However, the transition state structures determined by ab initio calculations change only slightly in the presence of a highly polar solvent as compared with the gas phase. We also calibrated the PM3 method for future study of an enzymatic SN2 displacement ...Continue Reading

References

May 5, 1995·The Journal of Biological Chemistry·F PriesD B Janssen
Jun 1, 1996·Current Opinion in Biotechnology·T Leisinger

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Citations

Apr 6, 2004·Current Opinion in Chemical Biology·Dick B Janssen
May 30, 1998·Proceedings of the National Academy of Sciences of the United States of America·A Warshel, J Florián
Aug 30, 2000·Proceedings of the National Academy of Sciences of the United States of America·E Y LauT C Bruice
Aug 5, 1997·Proceedings of the National Academy of Sciences of the United States of America·F C LightstoneT C Bruice
Jun 25, 2009·Chemistry : a European Journal·Takashi KamachiKazunari Yoshizawa
Jul 17, 2012·Physical Chemistry Chemical Physics : PCCP·Jimmy Heimdal, Ulf Ryde
Aug 10, 2006·Chemical Reviews·Jiali GaoDonald G Truhlar
Feb 11, 2005·Journal of the American Chemical Society·Alejandro SorianoManuel F Ruiz-López
Feb 14, 2006·The Journal of Physical Chemistry. B·Edina RostaArieh Warshel

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