Mechanism of S(H)2 reactions of disulfides: Frontside vs backside, stepwise vs concerted

Krenske, Elizabeth H., Pryor, William A. and Houk, K. N. (2009) Mechanism of S(H)2 reactions of disulfides: Frontside vs backside, stepwise vs concerted. Journal of Organic Chemistry, 74 15: 5356-5360. doi:10.1021/jo900834m


Author Krenske, Elizabeth H.
Pryor, William A.
Houk, K. N.
Title Mechanism of S(H)2 reactions of disulfides: Frontside vs backside, stepwise vs concerted
Formatted title
Mechanism of SH2 reactions of disulfides: Frontside vs backside, stepwise vs concerted
Journal name Journal of Organic Chemistry   Check publisher's open access policy
ISSN 0022-3263
1520-6904
Publication date 2009-08-07
Sub-type Article (original research)
DOI 10.1021/jo900834m
Volume 74
Issue 15
Start page 5356
End page 5360
Total pages 5
Place of publication Washington, United States
Publisher American Chemical Society
Language eng
Formatted abstract
Density functional theory calculations indicate that the SH2 reactions of disulfides with alkyl or aryl radicals take place via concerted backside displacement. The activation energies for reactions of Me• with RSSR (R = Me, Et, iPr, tBu) increase with the size of R, since larger R groups prevent the formation of an ideal geometry for SOMO−LUMO overlap. Frontside transition states can also be located, but these lie at least 11 kcal mol−1 above the corresponding backside transition states.
Keyword Density functional theory
active site residues
Nucleophilic-substitution
Homolytic substitution
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ

Document type: Journal Article
Sub-type: Article (original research)
Collection: School of Chemistry and Molecular Biosciences
 
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