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Nickel-Catalyzed Cross-Electrophile Coupling : = Methodology Development and Mechanistic Insights.

Record Type:	Language materials, manuscript : Monograph/item
Title/Author:	Nickel-Catalyzed Cross-Electrophile Coupling :/
Reminder of title:	Methodology Development and Mechanistic Insights.
Author:	Su, Zhi-Ming.
Description:	1 online resource (397 pages)
Notes:	Source: Dissertations Abstracts International, Volume: 86-01, Section: B.
Contained By:	Dissertations Abstracts International86-01B.
Subject:	Chemistry. -
Online resource:	click for full text (PQDT)
ISBN:	9798383228388

Nickel-Catalyzed Cross-Electrophile Coupling : = Methodology Development and Mechanistic Insights.
Su, Zhi-Ming.

Nickel-Catalyzed Cross-Electrophile Coupling :Methodology Development and Mechanistic Insights. - 1 online resource (397 pages)

Source: Dissertations Abstracts International, Volume: 86-01, Section: B.

Thesis (Ph.D.)--The University of Wisconsin - Madison, 2024.

Includes bibliographical references

Transition metal-catalyzed coupling reactions are the predominant methods for carbon-carbon bond formation in synthetic chemistry. Nickel-catalyzed cross-electrophile coupling (XEC) reactions have emerged as a promising alternative to conventional cross-coupling strategies that employ organometallic nucleophiles as coupling partners. Ni-catalyzed XEC reactions feature the direct coupling of two electrophiles enabled by Ni-catalysis that requires a stoichiometric source of electrons from chemical reductants or electroreduction. This strategy offers several benefits, such as the utilization of stable and widely available carbon electrophiles, operational simplicity, and great functional group tolerance. Consequently, notable advancements in Ni-catalyzed XEC reactions have been achieved over the past decades. This thesis describes the efforts towards the development, mechanistic understanding, and application of Ni-catalyzed XEC methods.Chapter 1 provides a high-level overview of Ni-catalyzed XEC reactions, including their first disclosures, development, and current state of the art. Reaction mechanisms and strategies for achieving cross-selectivity in Ni-catalyzed XEC reactions are also discussed.Chapter 2 discloses an electrochemical method that converts lignin-derived aromatic compounds into a collective of substituted biphenyl-4,4'-dicarboxylic acid (BPDA) derivatives via Ni- and Ni/Pd-catalyzed XEC. The synergy between chemical and electrochemical conditions is highlighted, showing that high-throughput experimentation with chemical reductants enables rapid catalyst discovery while electrochemistry improves reaction yields and/or facilitates implementation on larger scale. The resultant BPDA derivatives exhibit improved poly(vinyl chloride) (PVC) plasticizer performance and reduced toxicity relative to a commercial plasticizer.Chapter 3 describes the application of open-circuit potential measurements to determine the redox potentials of metal reductants in organic solutions. Different organic solvents and reaction additives are shown to significantly impact the thermodynamic potentials of metal reductants. Fundamental insights can be gained through the study of the relationship between reductant redox potentials and critical redox processes in XEC reactions. Finally, Ni-catalyzed XEC of N-alkyl-2,4,6-triphenylpyridinium reagents (Katritzky salts) with aryl halides is used to demonstrate how some of the limitations related to using metal reductants can be overcome by highly tunable electrochemical reduction.Chapter 4 details the development of a general strategy for the XEC of heteroaryl chlorides with aryl bromides via Ni-catalysis. Two sets of reaction conditions (A and B) have been identified to enable the coupling of a variety of heteroaryl chlorides and aryl bromides containing an array of functional groups and steric environments. Condition A is particularly effective for the coupling of 2-chloropyridines with aryl bromides. Mechanistic investigations into condition A suggest a Ni-catalyzed in situ aryl-zinc formation, followed by a Ni-catalyzed cross-coupling between aryl-zinc and 2-chloropyridines. Condition B is usually preferred for the XEC of diazaheteroaryl chlorides with aryl bromides. In this case, preliminary studies reveal the synergistic effects of NaI and FeBr2 to match the relative reactivity of the two coupling partners and achieve high cross-selectivity.Collectively, the studies presented herein are envisioned to enable the utilization of a broader scope of electrophiles in Ni-catalyzed XEC reactions and facilitate a better mechanistic understanding.

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

Mode of access: World Wide Web

ISBN: 9798383228388Subjects--Topical Terms:

593913
Chemistry.
Subjects--Index Terms:

CatalysisIndex Terms--Genre/Form:

554714
Electronic books.

Nickel-Catalyzed Cross-Electrophile Coupling : = Methodology Development and Mechanistic Insights.
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520 $a Transition metal-catalyzed coupling reactions are the predominant methods for carbon-carbon bond formation in synthetic chemistry. Nickel-catalyzed cross-electrophile coupling (XEC) reactions have emerged as a promising alternative to conventional cross-coupling strategies that employ organometallic nucleophiles as coupling partners. Ni-catalyzed XEC reactions feature the direct coupling of two electrophiles enabled by Ni-catalysis that requires a stoichiometric source of electrons from chemical reductants or electroreduction. This strategy offers several benefits, such as the utilization of stable and widely available carbon electrophiles, operational simplicity, and great functional group tolerance. Consequently, notable advancements in Ni-catalyzed XEC reactions have been achieved over the past decades. This thesis describes the efforts towards the development, mechanistic understanding, and application of Ni-catalyzed XEC methods.Chapter 1 provides a high-level overview of Ni-catalyzed XEC reactions, including their first disclosures, development, and current state of the art. Reaction mechanisms and strategies for achieving cross-selectivity in Ni-catalyzed XEC reactions are also discussed.Chapter 2 discloses an electrochemical method that converts lignin-derived aromatic compounds into a collective of substituted biphenyl-4,4'-dicarboxylic acid (BPDA) derivatives via Ni- and Ni/Pd-catalyzed XEC. The synergy between chemical and electrochemical conditions is highlighted, showing that high-throughput experimentation with chemical reductants enables rapid catalyst discovery while electrochemistry improves reaction yields and/or facilitates implementation on larger scale. The resultant BPDA derivatives exhibit improved poly(vinyl chloride) (PVC) plasticizer performance and reduced toxicity relative to a commercial plasticizer.Chapter 3 describes the application of open-circuit potential measurements to determine the redox potentials of metal reductants in organic solutions. Different organic solvents and reaction additives are shown to significantly impact the thermodynamic potentials of metal reductants. Fundamental insights can be gained through the study of the relationship between reductant redox potentials and critical redox processes in XEC reactions. Finally, Ni-catalyzed XEC of N-alkyl-2,4,6-triphenylpyridinium reagents (Katritzky salts) with aryl halides is used to demonstrate how some of the limitations related to using metal reductants can be overcome by highly tunable electrochemical reduction.Chapter 4 details the development of a general strategy for the XEC of heteroaryl chlorides with aryl bromides via Ni-catalysis. Two sets of reaction conditions (A and B) have been identified to enable the coupling of a variety of heteroaryl chlorides and aryl bromides containing an array of functional groups and steric environments. Condition A is particularly effective for the coupling of 2-chloropyridines with aryl bromides. Mechanistic investigations into condition A suggest a Ni-catalyzed in situ aryl-zinc formation, followed by a Ni-catalyzed cross-coupling between aryl-zinc and 2-chloropyridines. Condition B is usually preferred for the XEC of diazaheteroaryl chlorides with aryl bromides. In this case, preliminary studies reveal the synergistic effects of NaI and FeBr2 to match the relative reactivity of the two coupling partners and achieve high cross-selectivity.Collectively, the studies presented herein are envisioned to enable the utilization of a broader scope of electrophiles in Ni-catalyzed XEC reactions and facilitate a better mechanistic understanding.
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