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

Buchanan, Travis Lamonte

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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

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

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Copyright 2021 Travis Buchanan

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