NDLI: The Mechanism of SN2 Disulfide Bond Cleavage by Phosphorous Nucleophiles. Implications for Biochemical Disulfide Reducing Agents

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The Mechanism of SN2 Disulfide Bond Cleavage by Phosphorous Nucleophiles. Implications for Biochemical Disulfide Reducing Agents

Content Provider	PubMed Central
Author	Dmitrenko, Olga Thorpe, Colin Bach, Robert D.
Abstract	The B3LYP variant of DFT has been used to study the mechanism of S-S bond scission in dimethyl disulfide by phosphorus nucleophile, trimethylphospine (TMP). The reaction is highly endothermic in the gas phase and requires significant external stabilization of the charged products. DFT calculations (B3LYP) were performed with explicit (water molecules added) and implicit solvent corrections (COSMO model). The transition structures for this SN2 displacement reaction in a number of model systems have been located and fully characterized. The reaction barriers calculated with different approaches for different systems are quite close (around 11 kcal/mol). Remarkably, the calculations suggest, that the reaction is almost barrierless with respect to the pre-organized reaction complex and that the most of the activation energy is required to rearrange the disulfide and TMP to its most effective orientation for the SMe group transfer way. Different reactivities of different phosphorus nucleophiles were suggested to be the result of steric effects, as manifested largely by varying amounts of hindrance to solvation of the initial product phosphonium ion. These data indicate that the gas phase addition of a phosphine to the disulfide moiety will most likely form a phosphonium cation-thiolate anion salt, in the presence of four or more water molecules, that provide sufficient H-bonding stabilization to allow displacement of the thiolate anion, a normal uncomplicated SN2 transition state is to be expected.
Related Links	http://dx.doi.org/10.1021/jo071271w
Ending Page	8307
Page Count	10
Starting Page	8298
File Format	PDF
ISSN	00223263
e-ISSN	15206904
Journal	The Journal of organic chemistry
Issue Number	22
Volume Number	72
Language	English
Publisher Date	2007-10-01
Access Restriction	Open
Subject Keyword	Organic Chemistry Research in Higher Education
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry

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