Kevlishvili, Ilia
(2021)
Computational Studies of Transition Metal-Catalyzed Olefin Functionalization and Cross-Coupling Reactions.
Doctoral Dissertation, University of Pittsburgh.
(Unpublished)
This is the latest version of this item.
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Unpublished |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: |
|
| ETD Committee: |
|
| 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)
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