Journal article
Computational design of S-nitrosothiol "click" reactions
Journal of computational chemistry, Vol.34(18), pp.1527-1530
07/05/2013
Handle:
https://hdl.handle.net/2376/101751
PMID: 23553289
Abstract
To address a long-standing problem of finding efficient reactions for chemical labeling of protein-based S-nitrosothiols (RSNOs), we computationally explored hitherto unknown (3+2) cycloaddition RSNO reactions with alkynes and alkenes. Nonactivated RSNO cycloaddition reactions have high activation enthalpy (>20 kcal/mol at the CBS-QB3 level) and compete with alternative S-N bond insertion pathway. However, the (3+2) cycloaddition reaction barriers can be dramatically lowered by coordination of a Lewis acid to the N atom of the -SNO group. To exploit this effect, we propose to use reagents with Lewis acid and a strain-activated carbon-carbon multiple bond linked by a rigid scaffold, which can react with RSNOs with small activation enthalpies (∼5 kcal/mol) and high reaction exothermicities (∼40 kcal/mol). The proposed efficient RSNO cycloaddition reactions can be used for future development of practical RSNO labeling reactions.
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Details
- Title
- Computational design of S-nitrosothiol "click" reactions
- Creators
- Marat R Talipov - Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201, USADmitry G KhomyakovMing XianQadir K Timerghazin
- Publication Details
- Journal of computational chemistry, Vol.34(18), pp.1527-1530
- Academic Unit
- Chemistry, Department of
- Publisher
- United States
- Identifiers
- 99900546518001842
- Language
- English
- Resource Type
- Journal article