Cross-Coupling and Related Reactions: Connecting Past Success to the Development of New Reactions for the Future

Organometallics, Год журнала: 2018, Номер 38(1), С. 3 - 35

Опубликована: Ноя. 27, 2018

Cross-coupling reactions, which were discovered almost 50 years ago, are widely used in both industry and academia. Even though cross-coupling reactions now represent mature technology, there is still a significant amount of research this area that aims to improve the scope these develop more efficient catalysts, make practical. In tutorial, brief background provided, then major advances over last 20 described. These include development improved ligands precatalysts for extension much wider range electrophiles. For example, common with sp3-hybridized electrophiles as well ester, amide, ether, aziridine substrates. many modern substrates, traditional palladium-based catalysts less than systems based on first-row transition metals such nickel. Conventional have also inspired related cross-electrophile decarboxylative couplings metallaphotoredox chemistry. The new probably at same stage 30 tutorial highlights how strategies may be applicable making

Язык: Английский

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Base-free nickel-catalysed decarbonylative Suzuki–Miyaura coupling of acid fluorides

Nature, Год журнала: 2018, Номер 563(7729), С. 100 - 104

Опубликована: Окт. 23, 2018

Язык: Английский

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A general deoxygenation approach for synthesis of ketones from aromatic carboxylic acids and alkenes

Nature Communications, Год журнала: 2018, Номер 9(1)

Опубликована: Авг. 23, 2018

Abstract The construction of an aryl ketone structural unit by means catalytic carbon–carbon coupling reactions represents the state-of-the-art in organic chemistry. Herein we achieved direct deoxygenative synthesis aqueous solution from readily available aromatic carboxylic acids and alkenes, affording structurally diverse ketones moderate to good yields. Visible-light photoredox catalysis enables deoxygenation as acyl sources with triphenylphosphine a distinct perspective on activation. synthetic robustness is supported late-stage modification several pharmaceutical compounds complex molecules. This strategy further applied drug zolpidem three steps 50% total yield concise cyclophane-braced 18–20 membered macrocycloketones. It not only advancement for streamlined feedstock chemicals, but also radical activation mode beyond redox potential acids.

Язык: Английский

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Selective Decarbonylation via Transition-Metal-Catalyzed Carbon–Carbon Bond Cleavage

Chemical Reviews, Год журнала: 2020, Номер 121(1), С. 365 - 411

Опубликована: Июнь 16, 2020

Transition-metal-catalyzed decarbonylation via carbon–carbon bond cleavage is an essential synthetic methodology. Given the ubiquity of carbonyl compounds, selective decarbonylative process offers a distinct strategy using groups as "traceless handles". This reaction has been significantly developed in recent years many respects, including catalytic system development, mechanistic understanding, substrate scope, and application synthesis complex functional molecules. Therefore, this review aims to summarize progress on transition-metal-catalyzed process, from discovery new transformations understanding mechanisms, reveal great achievements potentials field. The contents are categorized by type chemical process. main challenges opportunities also examined with goal expanding range reactions.

Язык: Английский

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Insight into D_6h Symmetry: Targeting Strong Axiality in Stable Dysprosium(III) Hexagonal Bipyramidal Single‐Ion Magnets

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(40), С. 14146 - 14151

Опубликована: Июль 25, 2019

Abstract Following a novel synthetic strategy where the strong uniaxial ligand field generated by Ph 3 SiO − (Ph =anion of triphenylsilanol) and 2,4‐di‐ t Bu‐PhO (2,4‐di‐ tert butylphenol) ligands combined with weak equatorial L N6 , leads to [Dy III (L )(2,4‐di‐ Bu‐PhO) 2 ](PF 6 ) ( 1 ), )(Ph SiO) ](BPh 4 hexagonal bipyramidal dysprosium(III) single‐molecule magnets (SMMs) high anisotropy barriers U eff =973 K for =1080 =1124 under zero applied dc field. Ab initio calculations predict that dominant magnetization reversal barrier these complexes expands up 3rd Kramers doublet, thus revealing first time exceptional magnetic even six donor atoms fail negate, opening possibility other higher‐order symmetry SMMs.

Язык: Английский

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Trends in the Usage of Bidentate Phosphines as Ligands in Nickel Catalysis

Chemical Reviews, Год журнала: 2020, Номер 120(13), С. 6124 - 6196

Опубликована: Июнь 3, 2020

A critically important process in catalysis is the formation of an active catalyst from combination a metal precursor and ligand, as efficacy this reaction governs amount catalyst. This Review comprehensive overview reactions catalyzed by nickel added bidentate phosphine, focusing on steps transforming precatalyst ligand into potential effects transformation catalysis. Reactions covered include common cross-coupling reactions, such Suzuki, Heck, Kumada, Negishi couplings, addition cycloadditions, C–H functionalizations, polymerizations, hydrogenations, reductive among others. Overall, most widely used with free phosphines Ni(cod)2, which accounts for ∼50% reports surveyed, distantly followed Ni(acac)2 Ni(OAc)2, account ∼10% each. By compiling these we have calculated statistics usage each Ni(cod)2 other sources. The are simple, relatively inexpensive ligands, DPPE, DCPE, DPPP, DPPB, along others more complex backbones, DPPF Xantphos. use expensive chiral scattered, but ligands BINAP, Me-Duphos, Josiphos, related analogs.

Язык: Английский

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Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Chinese Journal of Chemistry, Год журнала: 2020, Номер 38(11), С. 1371 - 1394

Опубликована: Июнь 16, 2020

As a straightforward strategy for rapidly increasing molecular complexity, dicarbofunctionalization of alkenes has attracted substantial interests organic synthesis, medicine chemistry, and materials science. Nickel‐catalyzed cascade dicarbofunctionalizations have been flourished in this area recently, nickel‐mediated radical pathways particularly offer new opportunities conjunctive cross‐couplings with alkyl coupling partners. Herein, we give comprehensive review nickel‐catalyzed through historical perspective, including intermolecular three‐component reactions intramolecular reactions. Among the discussed review, carbometallation/cross‐coupling process addition/cross‐coupling are two major alkenes. The oxidative cyclization 1,2‐metallate shift processes also selectively discussed. These methods overcome limitations associated using noble metals field, providing an efficient access to structurally diversified molecules.

Язык: Английский

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Nickel and Palladium Catalysis: Stronger Demand than Ever

ACS Catalysis, Год журнала: 2022, Номер 12(2), С. 1180 - 1200

Опубликована: Янв. 5, 2022

Key similarities and differences of Pd Ni in catalytic systems are discussed. Overall, catalyze a vast number similar C–C C–heteroatom bond-forming reactions. However, the smaller atomic radius lower electronegativity Ni, as well more negative redox potentials low-valent species, often provide higher reactivity oxidative addition or insertion reactions persistence alkyl-Ni intermediates against β-hydrogen elimination, thus enabling activation reluctant electrophiles, including alkyl electrophiles. Another key point relates to stability open-shell electronic configurations Ni(I) Ni(III) compared with Pd(I) Pd(III). Nickel very involve interconvertible Ni(n+) active species variable oxidation states (Ni(0), Ni(I), Ni(II), Ni(III)). In contrast, involving Pd(III) still relatively less developed may require facilitation by special ligands merging photo- electrocatalysis. high Pd(n+) ensure their facile reduction Pd(0) under assistance numerous reagents solvents, providing concentrations molecular Pd1(0) complexes that can reversibly aggregate into Pdn clusters nanoparticles form cocktail Pdn(0) various nuclearities (i.e., values "n"). Ni(0) strong reductants; they sensitive deactivation air other oxidizers and, consequence, operate at catalyst loadings than palladium same The ease robustness versatility for catalysis, whereas variety enables diverse uncommon reactivity, albeit requiring efforts stabilization nickel systems. As discussion, we note easily "cocktail particles" different but (Pd1, Pdn, NPs), behave species" is stable nuclearities. Undoubtedly, there stronger demand ever not only develop improved efficient catalysts also understand mechanisms

Язык: Английский

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Suzuki–Miyaura cross coupling reaction: recent advancements in catalysis and organic synthesis

Catalysis Science & Technology, Год журнала: 2021, Номер 11(4), С. 1186 - 1221

Опубликована: Янв. 1, 2021

Suzuki–Miyaura cross coupling reaction (SMCR) – A milestone in the synthesis of C–C coupled compounds.

Язык: Английский

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A tautomeric ligand enables directed C‒H hydroxylation with molecular oxygen

Science, Год журнала: 2021, Номер 372(6549), С. 1452 - 1457

Опубликована: Июнь 24, 2021

Easing oxygen into arenes Although is all around us, it often surprisingly difficult to use for selective chemical oxidations, necessitating more expensive, wasteful alternatives. Li et al. report that careful ligand optimization produces palladium catalysts can efficiently activate hydroxylate a variety of aryl and heteroaromatic rings adjacent carboxylic acid substituent. The binds through pyridine pyridone components, the authors posit tautomerization between dative anionic coordination modes plays role in its effectiveness. Science , abg2362, this issue p. 1452

Язык: Английский

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