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Controlled α-Halogenation of Alkyl Sulfonamides and Development of Highly Active Bifunctional (Benz)Imidazolyl-Palladium Catalysts for Application in Sustainable Cross-Coupling Reactions.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Controlled α-Halogenation of Alkyl Sulfonamides and Development of Highly Active Bifunctional (Benz)Imidazolyl-Palladium Catalysts for Application in Sustainable Cross-Coupling Reactions.
Author:	Penn, Kyle Robert.
Published:	Ann Arbor : ProQuest Dissertations & Theses, 2023
Description:	132 p.
Notes:	Source: Dissertations Abstracts International, Volume: 85-04, Section: B.
Notes:	Advisor: Lindsay, Vincent;Lindsey, Jonathan S.;Proulx, Caroline;Pierce, Joshua G.;Heugten, Kimberly Ange-Van.
Contained By:	Dissertations Abstracts International85-04B.
Subject:	Acids.
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=30615851
ISBN:	9798380484107

Controlled α-Halogenation of Alkyl Sulfonamides and Development of Highly Active Bifunctional (Benz)Imidazolyl-Palladium Catalysts for Application in Sustainable Cross-Coupling Reactions.
Penn, Kyle Robert.

Controlled α-Halogenation of Alkyl Sulfonamides and Development of Highly Active Bifunctional (Benz)Imidazolyl-Palladium Catalysts for Application in Sustainable Cross-Coupling Reactions. - Ann Arbor : ProQuest Dissertations & Theses, 2023 - 132 p.

Source: Dissertations Abstracts International, Volume: 85-04, Section: B.

Thesis (Ph.D.)--North Carolina State University, 2023.

This item must not be sold to any third party vendors.

Transition-metal-catalyzed cross-coupling reactions are some of the most valuable and synthetically productive steps in the formation of organic compounds and materials relevant to an array of chemical industries. The Suzuki-Miyaura Coupling (SMC) specifically, is the single most commonly used carbon–carbon bond forming reaction in the pharmaceutical industry. Historically, improvements in Suzuki-Miyaura coupling reactions have often been accomplished by increasing the reactivity and stability of the metal catalysts by use of increasingly more effective ligands. In this work, a family of air- and moisture-stable dinuclear 2- benzimidazolylpalladium complexes, known to act as highly active bifunctional catalysts for sustainable cross-coupling reactions, is expanded upon and structure-activity relationships are studied and defined with respect to the catalysts’ performance in Suzuki-Miyaura Coupling (SMC) reactions. New understanding of structure-activity trends is leveraged to develop a more active catalyst capable of catalyzing the Suzuki coupling of aryl bromides as well as aryl chlorides efficiently and with good functional group compatibility in alcohol solvents at catalyst loadings of 0.003 mol% (60 ppm Pd) for aryl bromides and as low as 0.1 mol% (2000 ppm Pd) for aryl chlorides.Bis(azolium)dichloride salts constitute stable and convenient precursors for metal bis(carbenes) as ligands for a wide range of metal-catalyzed processes. However, the synthesis of such salts is often inefficient in part due to the low reactivity of dichloroalkanes in nucleophilic substitution reactions. New reaction kinetics and mechanistic studies in the literature on pyridine derivatives have inspired us to develop a novel method for the improved synthesis of bis(azolium) chloride salts in excellent yields, applicable to a wide scope of heterocyclic cores. This method can also be applied to the direct synthesis of bis(NHC)-metal complexes in a one-pot reaction from imidazole derivatives.The sulfonamide functional group has many unique factors that can be leveraged for drug design, and some biologically relevant sulfonamide-containing compounds have been accessed from α-halogenated sulfonamide derivatives. However, synthesis of such derivatives is often difficult due to unselective polyhalogenation, often creating inseparable mixtures of product when base-mediated halogenation is attempted. In this work we developed new methods to selectively access these α-halogenated derivatives directly from alkyl sulfonamides.

ISBN: 9798380484107Subjects--Topical Terms:

329098
Acids.

Controlled α-Halogenation of Alkyl Sulfonamides and Development of Highly Active Bifunctional (Benz)Imidazolyl-Palladium Catalysts for Application in Sustainable Cross-Coupling Reactions.
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245 1 0 $a Controlled α-Halogenation of Alkyl Sulfonamides and Development of Highly Active Bifunctional (Benz)Imidazolyl-Palladium Catalysts for Application in Sustainable Cross-Coupling Reactions.
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300 $a 132 p.
500 $a Source: Dissertations Abstracts International, Volume: 85-04, Section: B.
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502 $a Thesis (Ph.D.)--North Carolina State University, 2023.
506 $a This item must not be sold to any third party vendors.
520 $a Transition-metal-catalyzed cross-coupling reactions are some of the most valuable and synthetically productive steps in the formation of organic compounds and materials relevant to an array of chemical industries. The Suzuki-Miyaura Coupling (SMC) specifically, is the single most commonly used carbon–carbon bond forming reaction in the pharmaceutical industry. Historically, improvements in Suzuki-Miyaura coupling reactions have often been accomplished by increasing the reactivity and stability of the metal catalysts by use of increasingly more effective ligands. In this work, a family of air- and moisture-stable dinuclear 2- benzimidazolylpalladium complexes, known to act as highly active bifunctional catalysts for sustainable cross-coupling reactions, is expanded upon and structure-activity relationships are studied and defined with respect to the catalysts’ performance in Suzuki-Miyaura Coupling (SMC) reactions. New understanding of structure-activity trends is leveraged to develop a more active catalyst capable of catalyzing the Suzuki coupling of aryl bromides as well as aryl chlorides efficiently and with good functional group compatibility in alcohol solvents at catalyst loadings of 0.003 mol% (60 ppm Pd) for aryl bromides and as low as 0.1 mol% (2000 ppm Pd) for aryl chlorides.Bis(azolium)dichloride salts constitute stable and convenient precursors for metal bis(carbenes) as ligands for a wide range of metal-catalyzed processes. However, the synthesis of such salts is often inefficient in part due to the low reactivity of dichloroalkanes in nucleophilic substitution reactions. New reaction kinetics and mechanistic studies in the literature on pyridine derivatives have inspired us to develop a novel method for the improved synthesis of bis(azolium) chloride salts in excellent yields, applicable to a wide scope of heterocyclic cores. This method can also be applied to the direct synthesis of bis(NHC)-metal complexes in a one-pot reaction from imidazole derivatives.The sulfonamide functional group has many unique factors that can be leveraged for drug design, and some biologically relevant sulfonamide-containing compounds have been accessed from α-halogenated sulfonamide derivatives. However, synthesis of such derivatives is often difficult due to unselective polyhalogenation, often creating inseparable mixtures of product when base-mediated halogenation is attempted. In this work we developed new methods to selectively access these α-halogenated derivatives directly from alkyl sulfonamides.
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