ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 31, Number 2
JKCSEZ 31(2)
April 20, 1987 

Sigmatropic rearrangement of cis and trans-2-methyl-N-phenyl-1,3-oxathiolane-2-acetamide (b) and (c) gave unisolable sulfenic acids (d) and (f), respectively. These sulfenic acids were confirmed by deuterium exchange reactions involving 2-methylene and 2-methyl groups. The reactions also showed that no isomerization between the cis and trans sulfoxides (b) and (c) occurred under neutral conditions. However, the isomerization took place in the presence of acid catalyst. Stereospecific recyclization of sulfenic acids to the sulfoxides is attributable to possible hydrogen bonding between sulfenyl oxygen and NH proton or it arises from the geometrical requirements of the reacting bond and atoms in the reverse sigmatropic rearrangement. In the oxidation of 1, 3-oxathiolane, cis sulfoxide (b) could be obtained selectively in high yield by using H2O2-benzene seleninic acid.