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New Radical Reactivity at the Interface of Synthetic Methodology Development and Computational Modeling

Chen, Andrew
http://orcid.org/0000-0003-2672-8959
http://rave.ohiolink.edu/etdc/view?acc_num=osu1593586492097279

Abstract Details

2020, Doctor of Philosophy, Ohio State University, Chemistry.
The products of chemical synthesis touch every aspect of life in a modern industrial world, from the materials in our devices and tools, to the fuels that power them, and the medicines that keep us healthy. Steady improvements in these chemistries yield commensurate gains in quality of life, and realizing those improvements is a fundamental drive for the discovery of new, efficient methods. Efficient synthesis enables the transfer of time and resources spent on preparing molecules instead to their study and application. Classical synthetic strategies involve iterative transformation of pre-installed functionality, which can be both laborious to perform and limiting to starting functional groups. This stepwise approach can be effectively side-stepped by transformation of ubiquitous and inert C-H bonds to desired motifs in a strategy known as C-H functionalization. While many different methods to effect C-H functionalization exist, perhaps the most direct is achieved via hydrogen atom abstraction to access reactive carbon-centered radicals. These radicals can be engaged with a variety of radical traps, generating a wide range of different bonds, and enabling more streamlined synthesis. In line with the spirit of more deliberately designed, and therefore efficient, synthesis, computational methods have become increasingly more popular and provide prospective insights into experimental design and reaction discovery. Retrospective study and analysis of known reactivity via computation modeling also provides a framework that synthetic chemists can leverage for the design of new chemistry. These insights are rendered with a level of detail that is either difficult to attain with traditional experiments (e.g. molecular structure, bond strengths, electronegativities, etc.) or impossible (e.g. transition state structures). The physical chemical parameters of radicals, in particular, can be well-modeled with the theoretical chemical approaches of density functional theory. The research presented herein describes: the modeling and characterization of reaction parameters for a variety of organic radicals and radical traps (Chapter 2); computational modeling to provide mechanistic insights and predictive selectivity for arene C-H functionalization (Chapter 3); a novel method to prepare azoles from commercially available nitriles, alcohols, and amines (Chapter 4); and mechanistic studies in an Ir/Cu dual-catalytic, triplet sensitization mediated, alcohol β C-H amination (Chapter 5).
David Nagib, Ph.D. (Advisor)
Dehua Pei, Ph.D. (Committee Member)
Craig Forsyth, Ph.D. (Committee Member)
Steffen Lindert, Ph.D. (Committee Member)
335 p.
Chemistry; Organic Chemistry
organic synthesis, radical chemistry, photoredox catalysis, computational chemistry, DFT, organic chemistry, methodology, C-H functionalization, asymmetric catalysis

Recommended Citations

Citations

  • Chen, A. (2020). New Radical Reactivity at the Interface of Synthetic Methodology Development and Computational Modeling [Doctoral dissertation, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1593586492097279

    APA Style (7th edition)

  • Chen, Andrew. New Radical Reactivity at the Interface of Synthetic Methodology Development and Computational Modeling. 2020. Ohio State University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1593586492097279.

    MLA Style (8th edition)

  • Chen, Andrew. "New Radical Reactivity at the Interface of Synthetic Methodology Development and Computational Modeling." Doctoral dissertation, Ohio State University, 2020. http://rave.ohiolink.edu/etdc/view?acc_num=osu1593586492097279

    Chicago Manual of Style (17th edition)

osu1593586492097279
107
© 2020, all rights reserved.
This open access ETD is published by The Ohio State University and OhioLINK.