R. Glass, M. Hojjatie, M. Sabahi
1990
Citations
0
Influential Citations
12
Citations
Journal
Journal of Organic Chemistry
Abstract
Title compound (I) was synthesized by amination of the lithium enolate of methyl 6-endo-(methylthio)bicyclo[2.2.1] heptane-2-endo-carboxylate with O-(mesitylenesulfonyl)hydroxylamine followed by hydrolysis. Its crystal and molecular structure was determined by single-crystal X-ray analysis. The structure is compared both with 6-exo-(methylthio)bicyclo[2.2.1]heptane-2-endo-carboxylic acid and the HBr salt of 2-exo-aminobicyclo[2.2.1]heptane-2-endo-carboxylic acid. Electrochemical oxidation of I in acetonitrile, using the technique of cyclic voltammetry, revealed two oxidation waves with peak potentials of 0.90 and 1.35 V. Controlled potential electrolysis of I provided the corresponding sulfoxides as a mixture of diastereomers (in 60 and 25-30% yield, respectively), which were also prepared by chemical oxidation, derivatized, separated, and characterized. The remarkable cathodic shift of 450 mV for 1c is ascribed to neighboring carboxylate participation in oxidation of the thioether moiety