Citation
Kuo, Elaine Y. (1993) I. Thermal cyclization of (Z)-1,2,4-heptatrien-6-yne. II. Studies directed toward the synthesis of neocarzinostatin chromophore. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/x7qa-8x77. https://resolver.caltech.edu/CaltechTHESIS:01102013-092055513
Abstract
The possibility that the hydrocarbon (Z)-1,2,4-heptatrien-6-yne might undergo a thermal cyclization to the biradical α,3-dehydroluene was considered. A methodology for the synthesis of (Z)-1,2,4-heptatrien-6-yne was developed wherein propargyl hydrazines, obtained from the corresponding propargyl alcohols, were oxidized to allenes with diethyl azodicarboxylate in good yields. The formation of products consistent with the intermediacy of the biradical α,3-dehydrotoluene is discussed.
In studies directed toward the total synthesis of neocarzinostatin chromophore, the attempted formation of the cyclononadiyne core of the molecule via the intramolecular insertion of an alkylidene carbene into an acetylenic carbon-hydrogen bond was investigated. The alkylidene carbene was generated from the appropriately functionalized cyclopentanone precursor with the reagent dimethyl diazomethylphosphonate (DAMP). While the identification of the reaction products was consistent with the formation of the desired carbene, the formation of the desired insertion product was not observed. In conjunction with studies seeking to synthesize neocarzinostatin chromophore via an intramolecular acetylide addition, the synthesis of an epoxy carbonate fragment to be used in the convergent synthesis of a suitable cyclization precursor is described, as well as initial efforts concerning glycosylation with a suitably protected N-methyl D-fucosamine derivative.
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) |
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Thesis Committee: |
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Defense Date: | 12 March 1993 |
Record Number: | CaltechTHESIS:01102013-092055513 |
Persistent URL: | https://resolver.caltech.edu/CaltechTHESIS:01102013-092055513 |
DOI: | 10.7907/x7qa-8x77 |
Default Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. |
ID Code: | 7387 |
Collection: | CaltechTHESIS |
Deposited By: | Benjamin Perez |
Deposited On: | 10 Jan 2013 18:27 |
Last Modified: | 09 Nov 2022 19:20 |
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