國立虎尾科技大學 |

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

紀錄類型:	書目-語言資料,手稿 : Monograph/item
正題名/作者:	Controlled α-Halogenation of Alkyl Sulfonamides and Development of Highly Active Bifunctional (Benz)Imidazolyl-Palladium Catalysts for Application in Sustainable Cross-Coupling Reactions./
作者:	Penn, Kyle Robert.
面頁冊數:	1 online resource (132 pages)
附註:	Source: Dissertations Abstracts International, Volume: 85-04, Section: B.
Contained By:	Dissertations Abstracts International85-04B.
標題:	Polymer chemistry. -
電子資源:	click for full text (PQDT)
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. - 1 online resource (132 pages)

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

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

Includes bibliographical references

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.

Electronic reproduction.
Ann Arbor, Mich. :
ProQuest,
2024

Mode of access: World Wide Web

ISBN: 9798380484107Subjects--Topical Terms:

1182163
Polymer chemistry.
Index Terms--Genre/Form:

554714
Electronic books.

Controlled α-Halogenation of Alkyl Sulfonamides and Development of Highly Active Bifunctional (Benz)Imidazolyl-Palladium Catalysts for Application in Sustainable Cross-Coupling Reactions.
LDR:04068ntm a22003857 4500 001 1142086
005 20240414211941.5
006 m o d
007 cr mn ---uuuuu
008 250605s2023 xx obm 000 0 eng d
020 $a 9798380484107
035 $a (MiAaPQ)AAI30615851
035 $a (MiAaPQ)NCState_Univ18402041017
035 $a AAI30615851
040 $a MiAaPQ $b eng $c MiAaPQ $d NTU
100 1 $a Penn, Kyle Robert. $3 1466260
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.
264 0 $c 2023
300 $a 1 online resource (132 pages)
336 $a text $b txt $2 rdacontent
337 $a computer $b c $2 rdamedia
338 $a online resource $b cr $2 rdacarrier
500 $a Source: Dissertations Abstracts International, Volume: 85-04, Section: B.
500 $a Advisor: Lindsay, Vincent;Lindsey, Jonathan S.;Proulx, Caroline;Pierce, Joshua G.;Heugten, Kimberly Ange-Van.
502 $a Thesis (Ph.D.)--North Carolina State University, 2023.
504 $a Includes bibliographical references
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.
533 $a Electronic reproduction. $b Ann Arbor, Mich. : $c ProQuest, $d 2024
538 $a Mode of access: World Wide Web
650 4 $a Polymer chemistry. $3 1182163
650 4 $a Plastics. $3 563477
650 4 $a Pharmaceutical sciences. $3 1180569
650 4 $a Medical imaging. $3 1180167
650 4 $a Chemistry. $3 593913
650 4 $a Polyethylene glycol. $3 792155
650 4 $a Catalysis. $3 673438
650 4 $a Chemical bonds. $3 654810
650 4 $a Alcohol. $3 654366
650 4 $a Flexibility. $3 1466262
650 4 $a Sustainability. $3 793436
650 4 $a Solvents. $3 891167
650 4 $a Carbon. $3 557161
650 4 $a Sodium. $3 1437786
650 4 $a Iodine. $3 1058936
650 4 $a Chloride. $3 1372665
650 4 $a Nitrogen. $3 1372799
650 4 $a Lithium. $3 904879
650 4 $a Potassium. $3 1372559
650 4 $a Chromatography. $3 783938
650 4 $a Fluorides. $3 901712
650 4 $a Decomposition. $3 1372547
650 4 $a Nuclear magnetic resonance--NMR. $3 1466261
650 4 $a Palladium. $3 674498
650 4 $a Reagents. $3 1372660
650 4 $a Acids. $3 906611
655 7 $a Electronic books. $2 local $3 554714
690 $a 0640
690 $a 0485
690 $a 0574
690 $a 0572
690 $a 0795
690 $a 0495
710 2 $a North Carolina State University. $3 845424
710 2 $a ProQuest Information and Learning Co. $3 1178819
773 0 $t Dissertations Abstracts International $g 85-04B.
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=30615851 $z click for full text (PQDT)