University of Illinois Urbana-Champaign

Hydroamination of terminal allylic imines, allylic amines, and internal and terminal homoallylic amines: Regioselective and regiodivergent transformations

Ensign, Seth Cody

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ENSIGN-DISSERTATION-2017.pdf

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https://hdl.handle.net/2142/99462

Description

Title
Hydroamination of terminal allylic imines, allylic amines, and internal and terminal homoallylic amines: Regioselective and regiodivergent transformations
Author(s)
Ensign, Seth Cody
Issue Date
2017-09-14
Director of Research (if dissertation) or Advisor (if thesis)
Hull, Kami L.
Doctoral Committee Chair(s)
Hull, Kami L.
Committee Member(s)
  • Fout, Alison R.
  • Moore, Jeffrey S.
  • White, M. Christina
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Date of Ingest
2018-03-13T17:29:02Z
Keyword(s)
  • Hydroamination
  • Rhodium
  • Iridium
  • Allylic amines
  • Allylic imines
  • Homoallylic amines
Abstract
C–N bonds are ubiquitous in organic chemistry. Mild methods that allow for the direct formation of this motif from readily accessible functional groups would represent a powerful advance in organic synthesis. The intermolecular hydroamination of alkenes and amines represents a novel approach towards these disconnections from readily accessible functional groups. This transformation can streamline the synthesis of complex molecules and often allows access to two regioisomers (Markovnikov and anti-Markovnikov) from one starting material. 1,2-diamines are a common motif in many organic molecules. However, their synthesis often involves a lengthy, multi-step synthetic sequence. We report the Rh- and Ir-catalyzed addition of secondary cyclic, secondary acyclic, and primary acyclic (both aryl and aliphatic) amines to allyl amine. This transformation is highly chemoselective, regioselective, functional group tolerant, and can be used to form trans-diamines with excellent selectivity. Future directions for this method, including anti-Markovnikov and/or asymmetric hydroamination are discussed. The anti-Markovnikov hydroamination of aliphatic alkenes is a significant challenge for organometallic chemists. These products are typically formed via formal hydroamination. We report the Rh-catalyzed anti-Markovnikov selective hydroamination of homoallylic amines to form 1,4-diamines with electron rich secondary cyclic and acyclic amine nucleophiles. This transformation is tolerant of a variety of substituents on the homoallylic amine and mechanistic studies on these substrates are summarized. The regiodivergent functionalization of a substrate is a powerful method in organic chemistry; in the hydroamination literature, this transformation typically requires activated alkenes (allenes, dienes, etc.) and is limited in scope. The regiodivergent intermolecular hydroamination of homoallylic amines to selectively form either 1,3- or 1,4-diamines is disclosed. This method features both novel aryl amine nucleophiles and catalysts to form the desired product. This transformation is demonstrated on both terminal and internal alkenes and future directions are proposed.
Graduation Semester
2017-12
Type of Resource
text
Permalink
http://hdl.handle.net/2142/99462
Copyright and License Information
Copyright 2017 Seth Ensign

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