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The Role of Organic Cocatalysts in Homogeneous and Heterogeneous Oxidations : = Thermodynamic Principles and Mechanistic Insights.

Record Type:	Electronic resources : Monograph/item
Title/Author:	The Role of Organic Cocatalysts in Homogeneous and Heterogeneous Oxidations :/
Reminder of title:	Thermodynamic Principles and Mechanistic Insights.
Author:	Stamoulis, Alexios G.
Description:	1 online resource (294 pages)
Notes:	Source: Dissertations Abstracts International, Volume: 84-12, Section: B.
Contained By:	Dissertations Abstracts International84-12B.
Subject:	Chemistry. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=30524036click for full text (PQDT)
ISBN:	9798379725891

The Role of Organic Cocatalysts in Homogeneous and Heterogeneous Oxidations : = Thermodynamic Principles and Mechanistic Insights.
Stamoulis, Alexios G.

The Role of Organic Cocatalysts in Homogeneous and Heterogeneous Oxidations :Thermodynamic Principles and Mechanistic Insights. - 1 online resource (294 pages)

Source: Dissertations Abstracts International, Volume: 84-12, Section: B.

Thesis (Ph.D.)--The University of Wisconsin - Madison, 2023.

Includes bibliographical references

Oxidation reactions are among the most important transformations in organic chemistry and have enormous potential to streamline the synthesis of complex organic molecules. Aerobic oxidations are especially appealing since they circumvent the use of toxic, stoichiometric reagents that result in poor atom economy and intractable waste. However, few aerobic oxidation methods employ catalysts with suitable stability, activity, and/or selectivity to impact industrial organic chemical synthesis. Metalloenzymes that catalyze selective aerobic oxidation reactions in nature often work cooperatively with redox-active cofactors and coenzymes to achieve efficient aerobic turnover and provide a valuable framework for development of new catalysts. Herein are reported studies of oxidation reactions featuring a homogeneous or heterogeneous catalyst working cooperatively with a homogeneous cocatalyst to enable efficient organic oxidation reactions. Chapter 1 highlights the challenges associated with developing efficient aerobic oxidation manifolds and analyzes the thermodynamic principles underlying catalytic aerobic oxidation reactions. A series of case studies are used to highlight the implications of catalyst and cocatalyst potentials on the activity and selectivity in the context of chemical synthesis. These insights are used as a backdrop for the content in subsequent chapters. Chapter 2 describes the first aerobic oxoammonium generation with a heterogeneous catalyst and lays the foundation for the content in Chapter 3, which discloses the first example of a metal on nitrogen-doped carbon (MNC) working cooperatively with a nitroxyl cocatalyst to effect alcohol oxidation. Chapter 4 details the development of an eminently scalable Pd/HQ-cocatalyzed cis-selective diacyloxylation of cyclohexadiene. Chapter 5 describes the study and development of a highly efficient palladium aerobic C-H arylation catalyst through the mechanistically-guided development of new quinone cocatalysts.

Electronic reproduction.
Ann Arbor, Mich. :
ProQuest,
2023

Mode of access: World Wide Web

ISBN: 9798379725891Subjects--Topical Terms:

516420
Chemistry.
Subjects--Index Terms:

AerobicIndex Terms--Genre/Form:

542853
Electronic books.

The Role of Organic Cocatalysts in Homogeneous and Heterogeneous Oxidations : = Thermodynamic Principles and Mechanistic Insights.
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520 $a Oxidation reactions are among the most important transformations in organic chemistry and have enormous potential to streamline the synthesis of complex organic molecules. Aerobic oxidations are especially appealing since they circumvent the use of toxic, stoichiometric reagents that result in poor atom economy and intractable waste. However, few aerobic oxidation methods employ catalysts with suitable stability, activity, and/or selectivity to impact industrial organic chemical synthesis. Metalloenzymes that catalyze selective aerobic oxidation reactions in nature often work cooperatively with redox-active cofactors and coenzymes to achieve efficient aerobic turnover and provide a valuable framework for development of new catalysts. Herein are reported studies of oxidation reactions featuring a homogeneous or heterogeneous catalyst working cooperatively with a homogeneous cocatalyst to enable efficient organic oxidation reactions. Chapter 1 highlights the challenges associated with developing efficient aerobic oxidation manifolds and analyzes the thermodynamic principles underlying catalytic aerobic oxidation reactions. A series of case studies are used to highlight the implications of catalyst and cocatalyst potentials on the activity and selectivity in the context of chemical synthesis. These insights are used as a backdrop for the content in subsequent chapters. Chapter 2 describes the first aerobic oxoammonium generation with a heterogeneous catalyst and lays the foundation for the content in Chapter 3, which discloses the first example of a metal on nitrogen-doped carbon (MNC) working cooperatively with a nitroxyl cocatalyst to effect alcohol oxidation. Chapter 4 details the development of an eminently scalable Pd/HQ-cocatalyzed cis-selective diacyloxylation of cyclohexadiene. Chapter 5 describes the study and development of a highly efficient palladium aerobic C-H arylation catalyst through the mechanistically-guided development of new quinone cocatalysts.
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