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The Structural Elucidation of a Proposed Intermediate in the Stereoselective Synthesis of dl-Desoxypodocarpic Acid

Citation

Grand, Paul Sheldon (1969) The Structural Elucidation of a Proposed Intermediate in the Stereoselective Synthesis of dl-Desoxypodocarpic Acid. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechTHESIS:02222016-105427770

Abstract

The hydroxyketone C-3, an intermediate in the stereo-selective total synthesis of dl-Desoxypodocarpic acid (ii), has been shown by both degradative and synthetic pathways to rearrange in the presence of base to diosphenol E-1 (5-isoabietic acid series). The exact spatial arrangements of the systems represented by formulas C-3 and E-1 have been investigated (as the p-bromobenzoates) by single-crystal X-ray diffraction analyses. The hydroxyketone F-1, the proposed intermediate in the rearrangement, has been synthesized. Its conversion to diosphenol E-1 has been studied, and a single-crystal analysis of the p-bromobenzoate derivative has been performed. The initially desired diosphenol C-6 has been prepared, and has been shown to be stable to the potassium t-butoxide rearrangement conditions. Oxidative cleavage of diosphenol E-1 and subsequent cyclization with the aid of polyphosphoric acid has been shown to lead to keto acid I-2 (benzobicyclo [3.3.1] nonane series) rather than keto acid H-2 (5-isoabietic acid series).

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:16 September 1968
Funders:
Funding AgencyGrant Number
NIHUNSPECIFIED
NSFUNSPECIFIED
CaltechUNSPECIFIED
Record Number:CaltechTHESIS:02222016-105427770
Persistent URL:http://resolver.caltech.edu/CaltechTHESIS:02222016-105427770
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:9573
Collection:CaltechTHESIS
Deposited By: Leslie Granillo
Deposited On:22 Feb 2016 21:16
Last Modified:30 Oct 2018 18:28

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