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Photochemical Formation and Reactivities of Substituted Oxathiiranes in Low‐Temperature Argon Matrices
Author(s) -
Reisenauer Hans Peter,
Mloston Grzegorz,
Romanski Jaroslaw,
Schreiner Peter R.
Publication year - 2011
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201100695
Subject(s) - chemistry , regioselectivity , yield (engineering) , argon , photodissociation , density functional theory , irradiation , photochemistry , matrix isolation , ring (chemistry) , matrix (chemical analysis) , computational chemistry , organic chemistry , catalysis , thermodynamics , physics , chromatography , nuclear physics
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 kcal mol –1 .