On the Rearrangement Reactions of Pregnanediol Disulfate to Δ13-Steroid, and Its 20-Isomeric Sulfate to D-Homosteroids (Clinical Analysis on Steroids. XLII)

SHINJI ITOH; HARUMI ICHIKAWA; HIDETOSHI TAKAGI; ITSUO YOSHIZAWA

doi:10.1248/cpb.36.4261

On the Rearrangement Reactions of Pregnanediol Disulfate to Δ¹³-Steroid, and Its 20-Isomeric Sulfate to D-Homosteroids (Clinical Analysis on Steroids. XLII)

SHINJI ITOH, HARUMI ICHIKAWA, HIDETOSHI TAKAGI, ITSUO YOSHIZAWA

Author information

Keywords: pregnanediol disulfate, 5β-pregnane-3α, 20βdiol disulfate, hydrolysis, D-homosteroid, steroidal carbocation, Δ¹³-steroid, rearrangement reaction

JOURNAL FREE ACCESS

1988 Volume 36 Issue 11 Pages 4261-4268

DOI https://doi.org/10.1248/cpb.36.4261

Details

Abstract

17α-Ethyl-17β-methyl-5β-pregn-13-en-3α-ol, a major hydrolysis product of pregnanediol disulfate in 3N hydrochloric acid at 95°C, was shown to be formed via two reaction pathways, a concerted mechanism and a stepwise mechanism involving the C₂₀-carbocation, in an approximate ratio of 75:25.
D-Homoannulation of the isomeric sulfate, 5β-pregnane-3α, 2β-diol disulfate, giving 17α-methyl-D-homo-5β-androstane-3α-17aβ-diol as a predominant product under the same hydrolysis conditions, was shown to occur mainly (ca.90%) by the concerted mechanism.

Corresponding author

Register with J-STAGE for free!