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.)) |
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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): |
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Thesis Committee: |
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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: | INVALID USER |
Deposited On: | 16 Jul 2014 20:39 |
Last Modified: | 09 Nov 2022 19:20 |
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