Synthetic and mechanistic studies to expand the scope of alkyne metathesis dynamic covalent chemistry

Pattillo, Christopher C.

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Description

Title

Synthetic and mechanistic studies to expand the scope of alkyne metathesis dynamic covalent chemistry

Author(s)

Pattillo, Christopher C.

Issue Date

2019-06-17

Director of Research (if dissertation) or Advisor (if thesis)

Moore, Jeffrey S.

Doctoral Committee Chair(s)

Denmark, Scott E.

Committee Member(s)

• Hergenrother, Paul J.
• Murphy, Catherine J.

Department of Study

Chemistry

Discipline

Chemistry

Degree Granting Institution

University of Illinois at Urbana-Champaign

Degree Name

Ph.D.

Degree Level

Dissertation

Keyword(s)

• Alkyne metathesis
• chemistry
• organic chemistry
• catalysis
• dynamic covalent chemistry

Abstract

Dynamic covalent chemistry (DCC) is a widely applied method for the synthesis of diverse molecular architectures and chemical libraries which are of broad interest in a number of chemical disciplines. As part of the greater subset of molecular self-assembly processes, DCC allows for the assembly of complex molecules from simpler precursors through reversible covalent reactions. Alkyne metathesis has emerged as one of the most frequently applied reactions for the synthesis of shape-persistent molecular architectures via DCC. The scope of alkyne metathesis DCC has been rapidly expanding thanks to the development of increasingly active and functional group tolerant catalyst systems and is thus attractive as a method to prepare functionally diverse and responsive molecules. The continued development of alkyne metathesis as a synthetic strategy relies on both an understanding of reaction pathways and the expansion of this method into new chemical space. The first section of this dissertation expands upon the synthetic scope of alkyne metathesis to combine orthogonal dynamic functionality into 3D molecular cages. This study outlines the first example of alkyne metathesis being combined with orthogonal dynamic chemistries and also demonstrates that orthogonal DCC is a useful method for generating 3D structures which can respond to chemical stimuli. The third chapter aims to study reaction pathways and intermediates in alkyne metathesis DCC through self-assembly of two-dimensional molecular ladders. By studying these self-assembly processes, we have gained further insights into reaction pathways and kinetic traps in these systems. These studies also help to elucidate some of the key differences observed in the reaction pathways of alkyne metathesis as opposed to other self-assembly processes. We anticipate that the results outlined in this dissertation will complement existing strategies for dynamic synthesis and provide additional insight in to the reactivity of these systems.

Graduation Semester

2019-08

Type of Resource

text

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Copyright 2019 Christopher Pattillo

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