Date of Award
Doctor of Philosophy
Dr. Robert E. Harmon
Dr. S. K. Gupta
Dr. Jochanan Stenesh
Dr. Donald C. Berndt
In our earlier work we demonstrated the usefulness of the acidcatalyzed reaction between N-(p -tolyl)diphenylketenimine (21) and dimethyl sulfoxide (DMSO) for the oxidation of secondary alcohols. This was exemplified by the oxidation of 2',3'-O-isopropylideneadenosine and other secondary alcohols.1 We have now extended this procedure to the oxidation of hydroxy-steroids.
Alkynylamines or ynamines can be written in two resonance forms: R-C≡C-N R'2 and R-C=C=NR'2. Because of the close similarity between the latter structure and the structure of a ketenimine (R2C=C=N-R') and the ability of sulfoxide-ketenimine to effect the oxidation of secondary alcohols, we explored the possibility of using the acid-catalyzed reaction between alkynylamine and DMSO for the oxidation of the hydroxy-steroids. The ynamines N,N-dimethylamino-phenylacetylene and N,N-diethylamino-1-propyne were used for this investigations.
In addition, we have investigated the mechanism of ketenimine-DMSO and ynamine-DMSO oxidations and compared them with the sulfoxide-carbodiimide oxidation.
Zenarosa, Carmen V., "Dimethyl Sulfoxide Oxydation of Hydroxy-Steroids and Studies on the Oxidation of the 5’–Hydroxy Group of Nucleosides" (1969). Dissertations. 3434.