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Computational Studies of Transition Metal-Catalyzed Olefin Functionalization and Cross-Coupling Reactions

Kevlishvili, Ilia (2021) Computational Studies of Transition Metal-Catalyzed Olefin Functionalization and Cross-Coupling Reactions. Doctoral Dissertation, University of Pittsburgh. (Unpublished)

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Transition metal-catalyzed reactions have become one of the most critical tools for organic chemists. In particular, olefin functionalization and cross-coupling reactions provide access to a wide array of interesting compounds. Understanding reaction mechanisms play a crucial role in discovering new reactions and increasing the selectivity and scope of existing reactions. However, experimental methods are often insufficient to understand key mechanistic insights, and new reaction discovery often relies on trial-and-error. To address these challenges, I present a series of density functional theory (DFT) calculations to study the reaction mechanisms of various transition metal-catalyzed olefin functionalization and cross-coupling reactions. I applied a wide variety of computational methods, including energy decomposition analysis (EDA), distortion-interaction analysis, ligand steric contour plots, and conformational sampling, to understand complex factors that could promote reactivity or selectivity, such as ligand and substrate effects, conformational flexibility of ligands and substrates, and solvent and additive effects. Insights into the factors that promote reactivity are then used for a mechanistically guided catalyst design for improving reactivity.
Specifically, these computational approaches were applied to study copper-catalyzed hydroamination of olefins, copper-catalyzed allylation of indazoles, palladium-catalyzed regio-divergent cross-coupling of 3,5-dibromo-pyrone, a series of cross-coupling reactions of carbohydrates, and tandem nickel/zinc-catalyzed boron insertion into alkyl ether bonds.


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Item Type: University of Pittsburgh ETD
Status: Unpublished
CreatorsEmailPitt UsernameORCID
Kevlishvili, Iliailk13@pitt.eduilk130000-0001-8133-4165
ETD Committee:
TitleMemberEmail AddressPitt UsernameORCID
Committee ChairLiu,
Committee MemberWang,
Committee MemberCurran,
Committee MemberKeith,
Date: 8 October 2021
Date Type: Publication
Defense Date: 1 June 2021
Approval Date: 8 October 2021
Submission Date: 4 June 2021
Access Restriction: No restriction; Release the ETD for access worldwide immediately.
Number of Pages: 193
Institution: University of Pittsburgh
Schools and Programs: Dietrich School of Arts and Sciences > Chemistry
Degree: PhD - Doctor of Philosophy
Thesis Type: Doctoral Dissertation
Refereed: Yes
Uncontrolled Keywords: Olefin functionalization, Cross-coupling, Computational, DFT, Mechanism, Ligand effects, Transition-metal
Date Deposited: 08 Oct 2021 19:13
Last Modified: 08 Oct 2021 19:13

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