Diversity oriented, computer guided catalyst design: Application of chemoinformatics to catalysis

Henle, Jeremy John

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https://hdl.handle.net/2142/101249 Copy

Description

Title

Diversity oriented, computer guided catalyst design: Application of chemoinformatics to catalysis

Author(s)

Henle, Jeremy John

Issue Date

2018-01-19

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

Denmark, Scott E.

Doctoral Committee Chair(s)

Denmark, Scott E.

Committee Member(s)

• Burke, Martin D.
• Silverman, Scott K.
• Pogorelov, Taras V.

Department of Study

Chemistry

Discipline

Chemistry

Degree Granting Institution

University of Illinois at Urbana-Champaign

Degree Name

Ph.D.

Degree Level

Dissertation

Keyword(s)

Chemoinformatics, Catalysis

Abstract

The first half of this thesis (Chapter 2 and 3) focus on the development and application of a diversity oriented, computer guided catalyst optimization chemoinformatic workflow. This process seeks to combine the power of chemoinformatic diversity analysis and QSAR modeling with diversity and discovery oriented synthesis to rapidly and efficiently design active and selective catalysts for unsolved problems and novel transformations in synthetic organic chemistry. Chapter 2 focuses on the iterations of development that have resulted in the current chemoinformatic workflow, and Chapter 3 focuses on applications of the chemoinformatic methods developed for the workflow towards problems in enantioselective catalysis. The second half of this thesis (Chapter 4) focuses on the use of chemoinformatics to develop design criteria for active phase-transfer catalysts. The most common parameter used to predict PTC rates, the ammonium ion accessibility, q, is defined in such a way that limits its use to straight-chain tetraalkylammonium catalysts. To find a general descriptor of rate, eight linear, symmetrical tetraalkylammonium cations were examined to determine if a model containing broadly applicable descriptors could be found. The catalytic activity of these salts was determined under PTC conditions (operating under an interfacial, transport-rate limiting mechanism) and was compared with these molecular descriptors. Models could be generated from the ammonium ion accessibility parameter q and the amphiphilic cross-sectional area descriptor (XSA), and each gave a correlative model predicting the rate of alkylation. However, a similar model cannot be generated from a descriptor that is a direct measure of ammonium ion accessibility, the solvent accessible ammonium surface area (NC4_SA). These models lead to the conclusion that q must approximate catalyst properties other than ammonium ion accessibility. Additionally, the relationship between XSA and rate demonstrates that XSA approximates the complex behavior of ammonium ions at the interfacial region of a biphasic system, allowing for its use as a general descriptor for transport-limiting PTC rate approximations

Graduation Semester

2018-05

Type of Resource

text

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http://hdl.handle.net/2142/101249

Copyright and License Information

Copyright 2018 Jeremy Henle

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