Water as the reaction medium in organic chemistry: from our worst enemy to our best friend

Chemical Science, Journal Year: 2021, Volume and Issue: 12(12), P. 4237 - 4266

Published: Jan. 1, 2021

A review presenting water as the logical reaction medium for future of organic chemistry. discussion is offered that covers both "on water" and "in phenomena, how playing unique roles in each, specifically with regard to its use synthesis.

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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The 2‐Pyridyl Problem: Challenging Nucleophiles in Cross‐Coupling Arylations

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(20), P. 11068 - 11091

Published: Sept. 17, 2020

Azine-containing biaryls are ubiquitous scaffolds in many areas of chemistry, and efficient methods for their synthesis continually desired. Pyridine rings prominent amongst these motifs. Transition-metal-catalysed cross-coupling reactions have been widely used functionalisation as they often provide a swift tuneable route to related biaryl scaffolds. However, 2-pyridine organometallics capricious coupling partners 2-pyridyl boron reagents particular notorious instability poor reactivity Suzuki-Miyaura reactions. The pyridine-containing is therefore limited, the formation unsymmetrical 2,2'-bis-pyridines scarce. This Review focuses on developed challenging nucleophiles with (hetero)aryl electrophiles, ranges from traditional processes alternative nucleophilic novel main group approaches.

Language: Английский

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Recent advances on micellar catalysis in water

Advances in Colloid and Interface Science, Journal Year: 2020, Volume and Issue: 287, P. 102299 - 102299

Published: Oct. 26, 2020

Language: Английский

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Zinc-free, Scalable Reductive Cross-Electrophile Coupling Driven by Electrochemistry in an Undivided Cell

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(20), P. 12617 - 12626

Published: Oct. 3, 2022

Nickel-catalyzed reductive cross-electrophile coupling reactions are becoming increasingly important in organic synthesis, but application at scale is limited by three interconnected challenges: a reliance on amide solvents (complicated workup, regulated), the generation of stoichiometric Zn salts isolation, waste disposal issue), and mixing/activation challenges zinc powder. We show here an electrochemical approach that addresses these issues: reaction works acetonitrile with diisopropylethylamine as terminal reductant simple undivided cell (graphite(+)/nickel foam(-)). The utilizes combination two ligands, 4,4'-di-

Language: Английский

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Pd-Catalyzed Cross-Couplings: On the Importance of the Catalyst Quantity Descriptors, mol % and ppm

Organic Process Research & Development, Journal Year: 2022, Volume and Issue: 26(8), P. 2240 - 2269

Published: July 11, 2022

This Review examines parts per million (ppm) palladium concentrations in catalytic cross-coupling reactions and their relationship with mole percentage (mol %). Most studies chemistry have historically focused on the concentration ratio between (pre)catalyst limiting reagent (substrate), expressed as mol %. Several recent papers outlined use of "ppm level" an alternative means describing reaction systems. led us to delve deeper into literature assess whether is a practically useful descriptor catalyst quantities palladium-catalyzed reactions. Indeed, we conjectured that many could, unknowingly, employed low levels" (pre)catalyst, generally, what would spread ppm look like across selection reported vast array literature. In few selected examples, examined other metal systems for comparison palladium.

Language: Английский

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Palladium-catalyzed micellar cross-couplings: An outlook

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 488, P. 215158 - 215158

Published: May 2, 2023

Language: Английский

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Recent Highlights in Micellar Catalysis: An Industrial Outlook

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(4), P. 816 - 830

Published: March 14, 2024

From the context of sustainability, contemporary synthetic organic chemistry practices require significant transformation, as indicated by various sustainability matrices like atom economy, process mass intensity (PMI), E-factor, and DOZN. These factors have evidently unveiled inherent inefficiencies intrinsic to conventional protocols identified solvents principal causative agent. In response, utilization water a primary reaction medium for transformations has emerged an appealing alternative. This approach flourished with emergence micellar catalysis, where amphiphilic molecules alter bulk aqueous medium's solvation properties promote desired chemical transformation under milder sustainable conditions. After 2010, this technology gained considerable momentum established foundational framework performing reactions conditions, consequently mitigating dependency on hazardous solvents. perspective, recent advances in field catalysis will be discussed industrial applications, along future directions challenges associated regime.

Language: Английский

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Selectivity in micellar catalysed reactions: The role of interfacial dipole, compartmentalisation, and specific interactions with the surfactants

Current Opinion in Colloid & Interface Science, Journal Year: 2023, Volume and Issue: 64, P. 101681 - 101681

Published: Feb. 13, 2023

Micellar catalysis is playing a major role in green chemistry with ever increasing applications the efficient and sustainable preparation of natural compounds, drugs, more recently organic semiconductors for printed electronics.Most contributions field focus on developments surfactants suitable formulative conditions capable reproducingand often improvingthe yield reactions commonly performed solvents.The real ambition micellar approach goes beyond improvement sustainability existing methods aims at mimicking not only efficiency but also selectivity enzymatic catalysis.This review summarizes relevant examples enabled, efficient, selective transformations, discusses different kind processes impacting product distribution depending details state achieved.

Language: Английский

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Development of a Deactivation-Resistant Dialkylbiarylphosphine Ligand for Pd-Catalyzed Arylation of Secondary Amines

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 17, 2024

Despite the prevalence of N-heteroarenes in small-molecule pharmaceuticals, Pd-catalyzed C-N cross-coupling reactions aryl halides and amines containing these rings remain challenging due to their ability displace supporting ligand via coordination metal center. To address this limitation, we report development a highly robust Pd catalyst supported by new dialkylbiarylphosphine ligand, FPhos. The FPhos-supported effectively resists N-heteroarene-mediated deactivation readily promote coupling between wide variety Lewis-basic secondary amines, including densely functionalized pharmaceuticals. Mechanistic structural investigations, as well principal component analysis density functional theory, elucidated two key design features that enable FPhos overcome limitations previous ligands. First, ligated complex is stabilized through its conformational preference for O-bound isomer, which likely N-heteroarenes. Second, 3',5'-disubstitution on non-phosphorus-containing ring creates ideal steric environment around center, facilitates binding larger while mitigating formation off-cycle palladacycle species.

Language: Английский

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