Density functional theory study of reactions of aromatic thiols and Angeli's salt

ORGN 506

Laura L. Serbulea, serbulea@chem.ucla.edu1, Kei Goto2, Jon M. Fukuto3, and K. N. Houk, houk@chem.ucla.edu1. (1) Department of Chemistry and Biochemistry, University of California, Los Angeles, 607 Charles E. Young Drive East, Los Angeles, CA 90095-1569, (2) Interactive Research Center of Science, Graduate School of Science and Engineering, Tokyo Institute of Technology, Tokyo, Japan, (3) Department of Molecular and Medical Pharmacology, University of California, Los Angeles, Los Angeles, CA 90095-1735

Theoretical investigations of the mechanism of sulfenic acid formation from hindered aromatic thiols (BpqSH) and Angeli's salt have been carried out using 2,6-dimethylthiophenol as the model compound. Different pathways to sulfenic acid formation have been studied. It was found that the reactions in aqueous solution of model thiol with both HNO, from decomposition of Angeli's salt, and Angeli's salt anion (N2O32-) are slightly exergonic (-3.4 and -6.0 kcal/mol, respectively), and the kinetically most favorable pathway was predicted. Computations suggest that formation of sulfenic acid via hydrolysis of intermediate N-hydroxysulfenamide is not thermodynamically favorable.

 

Physical Organic Chemistry, Metal-Mediated Reactions, Asymmetric Reactions and Syntheses
8:00 PM-10:00 PM, Tuesday, August 21, 2007 BCEC -- Exhibit Hall - B2, Poster

Division of Organic Chemistry

The 234th ACS National Meeting, Boston, MA, August 19-23, 2007