University of Illinois Urbana-Champaign

Development of three-component alkene and 1,3-diene carbofunctionalization reactions

Buchanan, Travis Lamonte

Content Files
BUCHANAN-DISSERTATION-2021.pdf

Permalink

https://hdl.handle.net/2142/113151

Description

Title
Development of three-component alkene and 1,3-diene carbofunctionalization reactions
Author(s)
Buchanan, Travis Lamonte
Issue Date
2021-07-09
Director of Research (if dissertation) or Advisor (if thesis)
Hull, Kami L
Doctoral Committee Chair(s)
Hull, Kami L
Committee Member(s)
  • Chan, Jefferson
  • Girolami, Gregory S
  • Zimmerman, Steven C
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
2022-01-12T22:35:04Z
Keyword(s)
  • alkene difunctionalization
  • copper
  • catalysis
  • carboamination
Abstract
Given the prevalence of nitrogen-containing molecules in pharmaceuticals and agrochemicals, the development of efficient amination reactions is an essential research effort within the broad confines of organic method development. The ever-increasing complexity of the molecular structures used to treat human illness demands that novel transformations utilize mild reaction conditions, tolerate preexisting functionality, and rapidly produce structural complexity from accessible functionality. Furthermore, given the potential of novel strategic advances to productively alter the logic of complex molecule synthesis, the establishment of unintuitive retrosynthetic disconnections to achieve orthogonal means of access to desirable structures is of intense interest. In accord with these demands, we have developed a three-component alkene carboamination reaction. This system offers access to complex amine products from simple starting materials and proceeds under mild reaction conditions. Critically, this transformation combines disconnected carbon, nitrogen, and alkene moieties as independent reaction components, thus enabling the modular assembly of structurally diverse amines from a single reaction system. The discovery, development, and assessment of this system is detailed in the first chapter of this document. In the second chapter, the expansion of this system to achieve a general alkene carbofunctionalization system is explored, revealing that this strategy is capable of delivering carboesterification, carboetherification, and carboarylation products in addition to complex amines. The final chapter of this dissertation explores the development of a novel strategy for accessing allylic amines via a three-component 1,3-diene carboamination reaction. Utilizing many of the principles uncovered while developing the alkene functionalization reactions of the prior chapters, this system facilitates modular access to allylic amines that does not require the manipulation of preexisting allylic functionality. The discovery, development, and assessment of this novel system with respect to several classes of 1,3-dienes is presented.
Graduation Semester
2021-08
Type of Resource
Thesis
Permalink
http://hdl.handle.net/2142/113151
Copyright and License Information
Copyright 2021 Travis Buchanan

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