Mechanism of SH2 Reactions of Disulfides: Frontside vs Backside, Stepwise vs Concerted
作者： Elizabeth H. Krenske , William A. Pryor , K. N. Houk
DOI: 10.1021/JO900834M
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摘要: 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 Me• RSSR (R = Me, Et, iPr, tBu) increase size R, since larger R groups prevent formation an ideal geometry SOMO−LUMO overlap. Frontside transition states can also be located, but these lie at least 11 kcal mol−1 above corresponding states.
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Martin Sadı́lek, František Tureček, Metastable states of dimethylsulfonium radical, (CH3)2SH·:: A neutralization–reionization mass spectrometric and ab initio computational study International Journal of Mass Spectrometry. ,vol. 185, pp. 639- 649 ,(1999) , 10.1016/S1387-3806(98)14147-7
Elke Anklam, Formation and characterization of 1-substituted 1,2-dithiolanyl radicals by laser flash photolysis Research on Chemical Intermediates. ,vol. 11, pp. 227- 234 ,(1989) , 10.1163/156856789X00348
William A. Pryor, Reactions of radicals. A comparison of peroxides and disulfides1a Tetrahedron Letters. ,vol. 4, pp. 1201- 1204 ,(1963) , 10.1016/S0040-4039(01)90803-2
Daniel H. Ess, K. N. Houk, Theory of 1,3-Dipolar Cycloadditions: Distortion/Interaction and Frontier Molecular Orbital Models Journal of the American Chemical Society. ,vol. 130, pp. 10187- 10198 ,(2008) , 10.1021/JA800009Z
Jennifer E. Lyons, Carl H. Schiesser, Homolytic substitution at sulfides and sulfoxides: an ab initio molecular orbital study Journal of The Chemical Society-perkin Transactions 1. pp. 1655- 1656 ,(1992) , 10.1039/P29920001655
Daniel H. Ess, Gavin O. Jones, K. N. Houk, Transition States of Strain-Promoted Metal-Free Click Chemistry: 1,3-Dipolar Cycloadditions of Phenyl Azide and Cyclooctynes Organic Letters. ,vol. 10, pp. 1633- 1636 ,(2008) , 10.1021/OL8003657
Kim F. Ferris, James A. Franz, Carlos Sosa, Rodney J. Bartlett, Alkyl radical displacement reactions at sulfur : on the question of intermediacy in alkylsulfuranyl radicals Journal of Organic Chemistry. ,vol. 57, pp. 777- 778 ,(1992) , 10.1021/JO00028A076
Steven M. Bachrach, Andrey Pereverzev, Competing elimination and substitution reactions of simple acyclic disulfides Organic and Biomolecular Chemistry. ,vol. 3, pp. 2095- 2101 ,(2005) , 10.1039/B501370D
Olga Dmitrenko, Colin Thorpe, Robert D. Bach, Mechanism of SN2 Disulfide Bond Cleavage by Phosphorus Nucleophiles. Implications for Biochemical Disulfide Reducing Agents The Journal of Organic Chemistry. ,vol. 72, pp. 8298- 8307 ,(2007) , 10.1021/JO071271W
Trang Dao, Justin L. Mynar, Steven M. Bachrach, Joseph M. Hayes, Density functional theory gas- and solution-phase study of nucleophilic substitution at di- and trisulfides Theoretical Chemistry Accounts. ,vol. 107, pp. 266- 271 ,(2002) , 10.1007/S00214-002-0323-4