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Enantiosclective Synthesis of Pyrroloindolines and Tryptophan Derivatives by an Asvmmetric Protonation Reaction

Citation

Repka, Lindsay Michelle (2014) Enantiosclective Synthesis of Pyrroloindolines and Tryptophan Derivatives by an Asvmmetric Protonation Reaction. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechTHESIS:08192013-205304543

Abstract

Pyrroloindoline and unnatural tryptophan motifs are important targets for synthesis based on their incorporation into a diverse array of biologically active natural products. Both types of alkaloids have also found applications as chiral catalysts and tryptophan derivatives are commonly employed as biological probes. On account of their applications, these frameworks have inspired the development of numerous enantioselective, catalytic reactions. In particular, the past few years have witnessed an impressive number of novel approaches for pyrroloindoline formation.

The first project described herein involves our contribution to pyrroloindoline research. We have developed an (R)-BINOL•SnCl4-catalyzed formal (3 + 2) cycloaddition reaction between 3-substituted indoles and 2-amidoacrylates that affords pyrroloindoline-2-carboxylates bearing an all-carbon quaternary center. Mechanistic studies have elucidated that the enantiodetermining step is a highly face-selective catalyst-controlled protonation reaction. The subsequent application of this asymmetric protonation strategy to the synthesis of a variety of enantioenriched tryptophan derivatives is also discussed.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:pyrroloindolines; tryptophan derivatives; enantioselective; catalytic methodology; BINOL
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Mixed availability, specified at file level
Research Advisor(s):
  • Reisman, Sarah E.
Thesis Committee:
  • Dougherty, Dennis A. (chair)
  • Reisman, Sarah E.
  • Bercaw, John E.
  • Stoltz, Brian M.
Defense Date:8 July 2013
Funders:
Funding AgencyGrant Number
California Institute of TechnologyUNSPECIFIED
ACS Division of Organic Chemistry (sponsored by Genentech)UNSPECIFIED
ACS Petroleum Research FoundationUNSPECIFIED
NIHNIGMS RGM097582A
The Baxter FoundationUNSPECIFIED
NSFDGE-1144469
NIHNS 34407
Record Number:CaltechTHESIS:08192013-205304543
Persistent URL:http://resolver.caltech.edu/CaltechTHESIS:08192013-205304543
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja107328gDOIPublished article - Ch. 2
http://dx.doi.org/10.1021/ja209390dDOIPublished article - Ch. 3
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:7929
Collection:CaltechTHESIS
Deposited By: Lindsay Repka
Deposited On:21 Aug 2013 22:35
Last Modified:06 Feb 2017 17:47

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