University of Illinois Urbana-Champaign

The development of a rhodium-catalyzed chemo- and stereoselective hydroamination for the synthesis of 1,2-diamines

Ickes, Andrew R

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ICKES-THESIS-2016.pdf

ICKES-THESIS-2016.pdf

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Title
The development of a rhodium-catalyzed chemo- and stereoselective hydroamination for the synthesis of 1,2-diamines
Author(s)
Ickes, Andrew R
Issue Date
2016-12-02
Director of Research (if dissertation) or Advisor (if thesis)
Hull, Kami
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
M.S.
Degree Level
Thesis
Date of Ingest
2017-03-01T17:01:51Z
Keyword(s)
  • rhodium
  • hydroamination
  • intermolecular
  • stereoselective
  • chemoselective
Abstract
Amines are a prominent functionality found throughout organic molecules, including pharmaceuticals, agrochemicals, organic materials, and organic dyes.1 However, incorporation of amines into organic frameworks in step and atom economical fashion remains a significant challenge to synthetic chemists.2–4 In chapter 1, the importance of a class of compounds, 1,2-diamines is reviewed. Herein, many marketed pharmaceuticals, potential therapeutics, and natural products bearing this motif of interest are discussed. Additionally, 1,2-diamines have been shown as ligands for catalysis. Due to this interest in the 1,2-diamine functionality, some current synthetic methods to access 1,2-diamines will be shown. Chapter 2 discusses the hypothesis that a Lewis basic functionality could coordinate to a metal center and allow a hydroamination reaction to occur. Hydroamination was seen as a beneficial strategy to synthesize 1,2-diamines as olefins and amines are reacted in an atom-economical fashion. Initial reaction discovery of the rhodium-catalyzed intermolecular hydroamination of N-allylimines will be shown as well as reaction development. It was found that modest to high yields and high diastereoselectivities were obtained to synthesize 1,2-diamines with this methodology. Further, reaction development of secondary and primary N-allylamines will be discussed. These substrates offer attractive methods toward synthesizing 1,2-diamines by being easy to access. When secondary N-allylamines are employed, good yield is obtained for the desired hydroamination reaction. Excitingly, primary N-allylamines were able to be used as substrates for this transformation. This substrate class offered the shortest reaction times and proved to be effective for a wide range of amine nucleophiles.
Graduation Semester
2016-12
Type of Resource
text
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http://hdl.handle.net/2142/95603
Copyright and License Information
Copyright 2016 Andrew Ickes

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