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

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.

Name thesis:degree_name

M.S.

Level thesis:degree_level

Thesis

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2017

Author dc:creator

• Ickes, Andrew R

Contributors dc:contributor

• Hull, Kami

• rhodium
• hydroamination
• intermolecular
• stereoselective
• chemoselective

Statement dc:rights

• Copyright 2016 Andrew Ickes

Language dc:language

en

Handle dc:identifier

http://hdl.handle.net/2142/95603

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/95603