Dimethyl Sulfoxide Oxydation of Hydroxy-Steroids and Studies on the Oxidation of the 5’–Hydroxy Group of Nucleosides

Author

Carmen V. Zenarosa, Western Michigan University

Date of Award

12-1969

Degree Name

Doctor of Philosophy

Department

Chemistry

First Advisor

Dr. Robert E. Harmon

Second Advisor

Dr. S. K. Gupta

Third Advisor

Dr. Jochanan Stenesh

Fourth Advisor

Dr. Donald C. Berndt

Abstract

Introduction

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.

Access Setting

Dissertation-Open Access

Recommended Citation

Zenarosa, Carmen V., "Dimethyl Sulfoxide Oxydation of Hydroxy-Steroids and Studies on the Oxidation of the 5’–Hydroxy Group of Nucleosides" (1969). Dissertations. 3434.
https://scholarworks.wmich.edu/dissertations/3434