THE CONVERSION OF ASPERULOSIDE TO AN ANALOG OF THE COREY LACTONE-ALDEHYDE INTERMEDIATE FOR PROSTAGLANDINS.

Title: THE CONVERSION OF ASPERULOSIDE TO AN ANALOG OF THE COREY LACTONE-ALDEHYDE INTERMEDIATE FOR PROSTAGLANDINS.
Identifier: AAI8119659
identifier: 8119659
Creator: HRABIE, JOSEPH ANTHONY.
Contributor: Prof. William Berkowitz
Date: 1981
Language: English
Publisher: City University of New York.
Subject: Chemistry, Organic
Abstract: A three-step conversion of asperuloside tetraacetate (34) to the 11-deoxy-11-hydroxymethyl anlog 71a of the Corey lactone aldehyde has been developed.;The key intermediate, dilactone 35, was formed from asperuloside tetraacetate in one step by treatment with iodine/pyridinium dichromate followed by washing with sodium thiosulfate solution. This was then converted to aldehyde 71a by hydrogenation over rhodium on carbon and hydrolysis in refluxing aqueous acetic acid. Wadsworth-Emmons reaction of 71a with dimenthyl 2-oxoheptylphosphonate gave 73 in excellent overall yield (from 34).;Since previous workers have converted 71b to PGE(,2), PGF(,2(alpha)) and their 11-hydroxymethyl homologs, application of similar procedures to 71a should produce the same prostaglandins.;Extensive investigation of the chemistry of asperuloside resulted in the preparation of the previously unreported dibromide (65) and tertiary alcohol (64) as well as other derivatives of this iridoid.
Type: dissertation
Source: PQT Legacy CUNY.xlsx
degree: Ph.D.
Program: Chemistry

Media: THE CONVERSION OF ASPERULOSIDE TO AN ANALOG OF THE COREY LACTONE-ALDEHYDE INTERMEDIATE FOR PROSTAGLANDINS.