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Part I. Efforts directed towards the total synthesis of shionone. Part II. Conversion of estrone to androst-4-EN-3-ONE: a new method for activating the C-9 and C-10 positions of estrogenic steroids for substitution

Citation

Kowalski, Conrad J. (1974) Part I. Efforts directed towards the total synthesis of shionone. Part II. Conversion of estrone to androst-4-EN-3-ONE: a new method for activating the C-9 and C-10 positions of estrogenic steroids for substitution. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/XM7S-7224. https://resolver.caltech.edu/CaltechTHESIS:07162014-113619903

Abstract

Part I: An approach to the total synthesis of the triterpene shionone is described, which proceeds through the tetracyclic ketone i. The shionone side chain has been attached to this key intermediate in 5 steps, affording the olefin 2 in 29% yield. A method for the stereo-specific introduction of the angular methyl group at C-5 of shionone has been developed on a model system. The attempted utilization of this method to convert olefin 2 into shionone is described.

Part II: A method has been developed for activating the C-9 and C-10 positions of estrogenic steroids for substitution. Estrone has been converted to 4β,5β-epoxy-10β-hydroxyestr-3-one; cleavage of this epoxyketone using an Eschenmoser procedure, and subsequent modification of the product afforded 4-seco-9-estren-3,5-dione 3-ethylene acetal. This versatile intermediate, suitable for substitution at the 9 and/or 10 position, was converted to androst-4-ene-3-one by known procedures.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Ireland, Robert E.
Thesis Committee:
  • Unknown, Unknown
Defense Date:26 October 1973
Record Number:CaltechTHESIS:07162014-113619903
Persistent URL:https://resolver.caltech.edu/CaltechTHESIS:07162014-113619903
DOI:10.7907/XM7S-7224
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:8543
Collection:CaltechTHESIS
Deposited By: John Wade
Deposited On:16 Jul 2014 20:39
Last Modified:21 Dec 2019 04:41

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