Journal article

Publication year: 2011

Pages: 6269-6275

Journal: European Journal of Organic Chemistry

Volume number: 2011

Issue number: 31

ISSN: 1434-193X

DOI Link: https://doi.org/10.1002/ejoc.201100695

Publisher: Wiley

Abstract: 
Thiocarbonyl S-oxides (sulfines) derived from aliphatic and cycloaliphatic thioketones were irradiated in argon matrices at 10 K, and the resulting oxathiiranes were identified by comparison of computed and experimental IR spectra. Upon photolysis at 10 K, depending on the substitution pattern, the oxathiiranes underwent either H-shift reactions or regioselective ring enlargements to form the corresponding thioesters. After warming of the matrix material to 38-40 K, the oxathiiranes underwent fast desulfurization to yield the corresponding ketones. Density functional theory (DFT) computations at the B3LYP/6-311+G(3df,3pd) level suggest that the desulfurizations of oxathiiranes occurred as bimolecular processes with activation enthalpies near 0 kcalmol(-1).

Harvard Citation style: Reisenauer, H., Mloston, G., Romanski, J. and Schreiner, P. (2011) Photochemical Formation and Reactivities of Substituted Oxathiiranes in Low-Temperature Argon Matrices, European Journal of Organic Chemistry, 2011(31), pp. 6269-6275. https://doi.org/10.1002/ejoc.201100695

APA Citation style: Reisenauer, H., Mloston, G., Romanski, J., & Schreiner, P. (2011). Photochemical Formation and Reactivities of Substituted Oxathiiranes in Low-Temperature Argon Matrices. European Journal of Organic Chemistry. 2011(31), 6269-6275. https://doi.org/10.1002/ejoc.201100695