Unusual oxidative transformations of a steroidal 16alpha,17alpha,22-triol
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Updated: Jun 19, 2026

Cellular Lipid Extraction for Targeted Stable Isotope Dilution Liquid Chromatography-Mass Spectrometry Analysis
Published on: November 17, 2011
Jacek W Morzycki1, José Oscar H Pérez-Díaz, Rosa Santillan
1Institute of Chemistry, University of Białystok, al. Piłsudskiego 11/4, 15-443 Białystok, Poland. morzycki@uwb.edu.pl
Abstract:
A number of unexpected reactions were observed during attempts to invert configuration at C16 in 16alpha,17alpha,22-triol 3a. The PDC oxidation of 3a produced the D-seco-aldehyde 4a. Analogous compound 4b was obtained by Swern oxidation of the 16alpha,17alpha-dihydroxy-22-O-TES-ether 3b in addition to the desired 16-ketone 7. The unprotected triol 3a yielded pentacyclic products 5 and 6 under similar conditions. The Mitsunobu reaction of the triol 3a afforded 16-ketone 8 with inverted configuration of the side chain. During heating of a solution of 3a in THF with NaH at reflux autoxidation to the 16-ketone cyclic hemiketal 5, identical to one of the Swern oxidation products, took place.
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