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Novel variants of the zwitterionic Claisen rearrangement and the total synthesis of erythronolide B

Citation

Dong, Vy Maria (2004) Novel variants of the zwitterionic Claisen rearrangement and the total synthesis of erythronolide B. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-02252004-175803

Abstract

This dissertation describes the development of three novel variants of the zwitterionic Claisen rearrangement. Initial studies demonstrate an efficient and diastereoselective ketene-Claisen rearrangement catalyzed by metal salts. This process involves the condensation of ketenes and allylic amines to form zwitterionic enolates which undergo [3,3]-sigmatropic rearrangements to afford alpha,beta-disubstituted-gamma,delta-unsaturated amides. The scope of this chemistry is further expanded through the development of a Lewis acid-catalyzed acyl-Claisen rearrangement which employs acid chlorides as ketene surrogates. Based on these studies, a new tandem acyl-Claisen rearrangement for the construction of structurally complex 1,7-dioxo-acyclic architectures is achieved. The versatility of this tandem transformation for macrolide antibiotic synthesis is demonstrated through a concise total synthesis of erythronolide B, in 24 linear steps.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:claisen; erythromycin; erythronolide; macrolide antibiotics; sigmatropic rearrangement; tandem; total synthesis
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Restricted to Caltech community only
Research Advisor(s):
  • MacMillan, David W. C.
Thesis Committee:
  • Dervan, Peter B. (chair)
  • MacMillan, David W. C.
  • Bercaw, John E.
  • Marcus, Rudolph A.
Defense Date:31 October 2003
Record Number:CaltechETD:etd-02252004-175803
Persistent URL:http://resolver.caltech.edu/CaltechETD:etd-02252004-175803
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:754
Collection:CaltechTHESIS
Deposited By: Imported from ETD-db
Deposited On:27 Feb 2004
Last Modified:26 Dec 2012 02:32

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