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 (Unpublished)

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Abstract

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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Details

Item Type:	University of Pittsburgh ETD
Status:	Unpublished
Creators/Authors:	Creators Email Pitt Username ORCID Kevlishvili, Ilia ilk13@pitt.edu ilk13 0000-0001-8133-4165
ETD Committee:	Title Member Email Address Pitt Username ORCID Committee Chair Liu, Peng pengliu@pitt.edu Committee Member Wang, Yiming ym.wang@pitt.edu Committee Member Curran, Dennis curran@pitt.edu Committee Member Keith, John jakeith@pitt.edu
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
URI:	http://d-scholarship.pitt.edu/id/eprint/41344

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• Computational Studies of Transition Metal-Catalyzed Olefin Functionalization and Cross-Coupling Reactions. (deposited 08 Oct 2021 19:13) [Currently Displayed]

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