Citation
Kieffer, Madeleine Eileen (2015) New Catalytic Methods for the Preparation of Tryptophans and Pyrroloindolines: Total Synthesis of (+)-Naseseazines A and B and (–)-Aspergilazine A. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/Z9X0650X. https://resolver.caltech.edu/CaltechTHESIS:06052015-132556787
Abstract
Tryptophan and unnatural tryptophan derivatives are important building blocks for the total synthesis of natural products, as well as the development of new drugs, biological probes, and chiral small molecule catalysts. This thesis describes various catalytic methods for the preparation of tryptophan derivatives as well as their functionalization and use in natural product total synthesis.
Herein, the tandem Friedel–Crafts conjugate addition/asymmetric protonation reaction between 2-substituted indoles and methyl 2-acetamidoacrylate to provide enantioenriched trytophans is reported. This method inspired further work in the area of transition metal catalyzed arylation reactions. We report the development of the coppercatalyzed arylation of tryptamine and tryptophan derivatives. The utility of these transformations is highlighted in the five-step syntheses of the natural products (+)-naseseazine A and B. Further work on the development of a mild and general Larock indolization protocol to access unnatural tryptophans is also discussed.
Item Type: | Thesis (Dissertation (Ph.D.)) | ||||||
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Subject Keywords: | catalysis, indole, tryptophan, pyrroloindoline, total synthesis | ||||||
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: | 21 May 2015 | ||||||
Funders: |
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Record Number: | CaltechTHESIS:06052015-132556787 | ||||||
Persistent URL: | https://resolver.caltech.edu/CaltechTHESIS:06052015-132556787 | ||||||
DOI: | 10.7907/Z9X0650X | ||||||
Default Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | ||||||
ID Code: | 8999 | ||||||
Collection: | CaltechTHESIS | ||||||
Deposited By: | Madeleine Kieffer | ||||||
Deposited On: | 05 Jun 2015 22:38 | ||||||
Last Modified: | 04 Oct 2019 00:08 |
Thesis Files
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PDF (Full Thesis with spectra)
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PDF (Title Page etc)
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PDF (Chapter 1)
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PDF (Chapter 2)
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PDF (Chapter 3)
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PDF (Chapter 4)
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