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New Catalytic Methods for the Preparation of Tryptophans and Pyrroloindolines: Total Synthesis of (+)-Naseseazines A and B and (–)-Aspergilazine A

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. http://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.))
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)
Research Advisor(s):
  • Reisman, Sarah E.
Thesis Committee:
  • Stoltz, Brian M. (chair)
  • Dougherty, Dennis A.
  • Peters, Jonas C.
  • Reisman, Sarah E.
Defense Date:21 May 2015
Funders:
Funding AgencyGrant Number
NIHRR027690
NSF Graduate Research Fellowship1144469
Record Number:CaltechTHESIS:06052015-132556787
Persistent URL:http://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:01 Jun 2016 20:36

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