Breaking and making of the S-S linkage via nucleophilic substitution. An ab initio study

Pál Császár, I. Csizmadia, Wladia Viviani, Michel Loos, Jean Louis Rivail, A. Perczel

Research output: Contribution to journalArticle

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Abstract

The energetics of nucleophilic opening and closing of protonated disulphide bridges formula presented has been studied for the case of two sulphur-containing (H2S and CH3SH) nucleophiles. The energetics of this reaction was compared to that of the nucleophilic opening and closing of disulphide bridges with thiolate ions: formula presented In the former case a not so good nucleophile is combined with an excellent leaving group, and in the latter case a superior nucleophile is combined with a relatively poor leaving group. The barrier heights for these SN2-type reactions were found to be comparable as calculated by ab initio MO methods. In addition, two oxygen-containing nucleophiles (H2O, HCONH-CH[CH2OH]-CONH2) have also been studied in the following reaction: formula presented The water molecule is not nucleophilic enough to open the disulphide bridge. However, in a serine residue, in which the oxygen of the side-chain OH group is activated through backbone/side-chain hydrogen bonding, the hydroxy group is sufficiently nucleophilic to open the disulphide bridge, just like the sulphur-containing nucleophiles mentioned above.

Original languageEnglish
Pages (from-to)107-122
Number of pages16
JournalJournal of Molecular Structure: THEOCHEM
Volume455
Issue number2-3
Publication statusPublished - Dec 18 1998

Fingerprint

Nucleophiles
nucleophiles
linkages
Disulfides
disulfides
Substitution reactions
substitutes
Sulfur
Plant shutdowns
closing
Oxygen
sulfur
Hydrogen Bonding
Serine
oxygen
Ions
Hydrogen bonds
Water
methylidyne
Molecules

Keywords

  • Energetics
  • Nucleophilic substitution
  • S-S linkage

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computational Theory and Mathematics
  • Atomic and Molecular Physics, and Optics

Cite this

Breaking and making of the S-S linkage via nucleophilic substitution. An ab initio study. / Császár, Pál; Csizmadia, I.; Viviani, Wladia; Loos, Michel; Rivail, Jean Louis; Perczel, A.

In: Journal of Molecular Structure: THEOCHEM, Vol. 455, No. 2-3, 18.12.1998, p. 107-122.

Research output: Contribution to journalArticle

Császár, Pál ; Csizmadia, I. ; Viviani, Wladia ; Loos, Michel ; Rivail, Jean Louis ; Perczel, A. / Breaking and making of the S-S linkage via nucleophilic substitution. An ab initio study. In: Journal of Molecular Structure: THEOCHEM. 1998 ; Vol. 455, No. 2-3. pp. 107-122.
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AU - Perczel, A.

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N2 - The energetics of nucleophilic opening and closing of protonated disulphide bridges formula presented has been studied for the case of two sulphur-containing (H2S and CH3SH) nucleophiles. The energetics of this reaction was compared to that of the nucleophilic opening and closing of disulphide bridges with thiolate ions: formula presented In the former case a not so good nucleophile is combined with an excellent leaving group, and in the latter case a superior nucleophile is combined with a relatively poor leaving group. The barrier heights for these SN2-type reactions were found to be comparable as calculated by ab initio MO methods. In addition, two oxygen-containing nucleophiles (H2O, HCONH-CH[CH2OH]-CONH2) have also been studied in the following reaction: formula presented The water molecule is not nucleophilic enough to open the disulphide bridge. However, in a serine residue, in which the oxygen of the side-chain OH group is activated through backbone/side-chain hydrogen bonding, the hydroxy group is sufficiently nucleophilic to open the disulphide bridge, just like the sulphur-containing nucleophiles mentioned above.

AB - The energetics of nucleophilic opening and closing of protonated disulphide bridges formula presented has been studied for the case of two sulphur-containing (H2S and CH3SH) nucleophiles. The energetics of this reaction was compared to that of the nucleophilic opening and closing of disulphide bridges with thiolate ions: formula presented In the former case a not so good nucleophile is combined with an excellent leaving group, and in the latter case a superior nucleophile is combined with a relatively poor leaving group. The barrier heights for these SN2-type reactions were found to be comparable as calculated by ab initio MO methods. In addition, two oxygen-containing nucleophiles (H2O, HCONH-CH[CH2OH]-CONH2) have also been studied in the following reaction: formula presented The water molecule is not nucleophilic enough to open the disulphide bridge. However, in a serine residue, in which the oxygen of the side-chain OH group is activated through backbone/side-chain hydrogen bonding, the hydroxy group is sufficiently nucleophilic to open the disulphide bridge, just like the sulphur-containing nucleophiles mentioned above.

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