Intramolecular Hydroamination of Alkynes Catalyzed by Silver-Phenanthroline Complexes

Doctoral Dissertation

Abstract

The intramolecular hydroamination reaction is among the more versatile means of forming nitrogen-containing hetereocycles, compounds of interest in a variety of chemical disciplines. While the reaction has been intensely studied, concerns still exist over its amenability to organic synthesis. This thesis details the implementation of a readily-recyclable silver-1,10-phenanthroline catalyst which has demonstrated high efficiency for the hydroamination of a variety of aminoalkynes. As a means for developing a protocol for enantioselective synthesis, the desymmetrization of a prochiral diyne was accomplished using the silver-1,10-phenanthroline catalyst. This desymmetrization creates chiral compounds, an occurrence not often observed in the alkyne hydroamination.

A separate project involved in the development of improved immunotherapies led us to develop and complete a synthesis of β-hydroxy-methionine. The third attempt via vinyl glycine eventually allowed for the completion of this molecule. It is planned for this amino acid derivative to be included in an antigenic peptide.

Attributes

Attribute NameValues
URN
  • etd-04152009-155232

Author Jeffrey Munson Carney
Advisor Paul Helquist
Contributor Olaf Wiest, Committee Member
Contributor Paul Helquist, Committee Chair
Contributor Marya Lieberman, Committee Member
Contributor Brian Baker, Committee Member
Degree Level Doctoral Dissertation
Degree Discipline Chemistry and Biochemistry
Degree Name PhD
Defense Date
  • 2009-03-02

Submission Date 2009-04-15
Country
  • United States of America

Subject
  • hydroamination

  • transition metal catalysis

  • synthesis

  • unnatural amino acid

  • ketoimine

  • prochiral aminodiyne

Publisher
  • University of Notre Dame

Language
  • English

Record Visibility and Access Public
Content License
  • All rights reserved

Departments and Units

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