Well-Defined Palladium(II)–NHC Precatalysts for Cross-Coupling Reactions of Amides and Esters by Selective N–C/O–C Cleavage

Accounts of Chemical Research, Journal Year: 2018, Volume and Issue: 51(10), P. 2589 - 2599

Published: Sept. 21, 2018

Transition-metal-catalyzed cross-coupling reactions represent a most powerful tool for the rapid construction of C-C and C-X bonds available to synthetic chemists. Recently, tremendous progress has been made in burgeoning area amides esters enabled by regio- chemoselective acyl (X = N, O) cleavage using well-defined Pd(II)-NHC complexes. The use N-heterocyclic carbenes as ligands palladium-catalyzed cross-couplings permits that were previously impossible palladium or could be achieved only under harsh conditions. These provide an attractive method chemists manipulate traditionally inert amide ester with broad generality inherent catalysis. Research stable electrophiles can broadly categorized type electrophile undergoing cross-coupling. Recent studies have shown transition-metal catalysis represents one straightforward wide-ranging ways manipulating classically into generic acyl-metal intermediates systematically exploited new paradigm organic synthesis. key achieving high chemoselectivity process is control amidic resonance (nN πC═O* conjugation, rotation ca. 15-20 kcal/mol planar amides), enabling oxidative addition N-C bond metal rational predictable manner. This mode extended C(acyl)-O aryl esters, where selective C-O accomplished through match nucleophilic catalysts. two types transition-metal-catalyzed concept chemistry because ubiquity precursors Furthermore, stability provides unprecedented opportunities orthogonal strategies presence other electrophiles. In this Account, we highlight advances taken place past few years field focusing on both (1) stereoelectronic properties complexes critical realize challenging manifold (2) role isomerization barrier broader sense, described here practical approach functionalize common functional groups synthesis establishes access enable nonconventional strategies.

Language: Английский

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Buchwald-Hartwig reaction: An overview

Journal of Organometallic Chemistry, Journal Year: 2018, Volume and Issue: 861, P. 17 - 104

Published: Feb. 21, 2018

Language: Английский

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Highly selective transition-metal-free transamidation of amides and amidation of esters at room temperature

Nature Communications, Journal Year: 2018, Volume and Issue: 9(1)

Published: Oct. 3, 2018

Abstract Amide chemistry has an essential role in the synthesis of high value molecules, such as pharmaceuticals, natural products, and fine chemicals. Over past years, several examples transamidation reactions have been reported. In general, transition-metal-based catalysts or harsh conditions are employed for these transformations due to unfavorable kinetics thermodynamics process. Herein, we report a significant advance this area present general method transition-metal-free amides amidation esters by highly selective acyl cleavage with non-nucleophilic amines at room temperature. contrast metal-catalyzed protocols, is operationally-simple, environmentally-friendly, operates under exceedingly mild conditions. The practical highlighted valuable yields. Considering key various branches chemical science, envision that broadly applicable will be great interest organic synthesis, drug discovery, biochemistry.

Language: Английский

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Amide Bond Activation: The Power of Resonance

Trends in Chemistry, Journal Year: 2020, Volume and Issue: 2(10), P. 914 - 928

Published: Sept. 21, 2020

Language: Английский

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Emerging Trends in Cross-Coupling: Twelve-Electron-Based L₁Pd(0) Catalysts, Their Mechanism of Action, and Selected Applications

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(23), P. 16983 - 17027

Published: Oct. 3, 2022

Monoligated palladium(0) species, L

Language: Английский

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Contemporary Approaches for Amide Bond Formation

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(24), P. 4359 - 4391

Published: Nov. 7, 2023

Abstract Amide bond construction has garnered significant interest in recent decades due to amides being one of the most prevalent functional groups among bioactive molecules. Out thirty‐seven new drugs approved by FDA 2022, eleven are small molecules containing at least amide bond. Additionally, there nineteen large as drugs, some which have peptide structures, and therefore, also bear bonds. In years, multiple teams embraced challenge developing more efficient methods for formation. This dedication led numerous publications appearing monthly prestigious journals, showcasing advancements this field. The primary goal review is present viable strategies constructing It crucial differentiate between formation synthesis; hence, focus on describing specific forming C(O)−N particular, concentrates developed within last six years. There a particular emphasis approaches that consider thought process when selecting starting materials groups. approach ensures coverage all common chemical transformations yield

Language: Английский

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Decarbonylative cross-coupling of amides

Organic & Biomolecular Chemistry, Journal Year: 2018, Volume and Issue: 16(43), P. 7998 - 8010

Published: Jan. 1, 2018

We present recent advances and key developments in the field of decarbonylative cross-coupling reactions amides by a formal double N–C/C–C bond activation as well discuss future challenges potential applications for this exciting field.

Language: Английский

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Recent Advances in the Metal‐Catalyzed Activation of Amide Bonds

Chemistry - An Asian Journal, Journal Year: 2018, Volume and Issue: 14(1), P. 76 - 93

Published: Nov. 14, 2018

Abstract The amide functional group is commonly found in peptides, proteins, pharmaceutical compounds, natural products, and polymers. synthesis of amides typically performed by using classical approaches that involve the reaction between a carboxylic acid an amine presence activator. Amides are thought to be inert group, because they unsusceptible nucleophile attack, owing their low electrophilicity. reason for this resistance clear: resonance stability bond. However, transition metal catalysis can circumvent selectively rupturing N−C bond amide, thereby facilitating further cross‐coupling or other reactions. In Focus Review, we discuss recent advances area present summary methods have been developed activating precious non‐precious metals.

Language: Английский

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Catalytic Isofunctional Reactions—Expanding the Repertoire of Shuttle and Metathesis Reactions

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 58(30), P. 10074 - 10103

Published: Sept. 7, 2018

Transfer hydrogenation, alkene metathesis, and alkyne metathesis possess great value to the synthetic chemistry community. One of key features these processes is their reversibility, which can be attributed presence same number type functional groups in both reactants products, making reactions isofunctional. These classic have recently inspired development novel shuttle that offer promise for chemistry. This Review describes systematically categorizes recent older examples other than transfer hydrogenation alkene/alkyne metathesis.

Language: Английский

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N‐Acyl‐Glutarimides: Privileged Scaffolds in Amide N–C Bond Cross‐Coupling

European Journal of Organic Chemistry, Journal Year: 2018, Volume and Issue: 2018(20-21), P. 2352 - 2365

Published: Feb. 14, 2018

In this Microreview, we describe the recent exciting developments in burgeoning area of amide N–C cross‐coupling enabled by bond twist N ‐acyl‐glutarimides. Since initial reports 2015, these amides have been demonstrated to be far most reactive derivatives biologically‐relevant manifold activation/cross‐coupling, thus stimulating development more than 10 previously unknown catalytic modes reactivity bond. The capacity ‐acyl‐glutarimides as privileged scaffolds expedite acyl and decarbonylative cross‐couplings cleavage is discussed.

Language: Английский

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