Nickel and Palladium Catalysis: Stronger Demand than Ever

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(2), P. 1180 - 1200

Published: Jan. 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

Language: Английский

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Activation of C–O and C–N Bonds Using Non-Precious-Metal Catalysis

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(20), P. 12109 - 12126

Published: Sept. 10, 2020

ADVERTISEMENT RETURN TO ISSUEPREVViewpointNEXTActivation of C–O and C–N Bonds Using Non-Precious-Metal CatalysisTimothy B. BoitTimothy BoitDepartment Chemistry Biochemistry, University California, Los Angeles, California 90095, United StatesMore by Timothy Boit, Ana S. BulgerAna BulgerDepartment Bulger, Jacob E. DanderJacob DanderDepartment Dander, Neil K. Garg*Neil GargDepartment States*E-mail: [email protected]More Garghttp://orcid.org/0000-0002-7793-2629Cite this: ACS Catal. 2020, 10, 20, 12109–12126Publication Date (Web):September 2020Publication History Received30 July 2020Published online10 September inissue 16 October 2020https://pubs.acs.org/doi/10.1021/acscatal.0c03334https://doi.org/10.1021/acscatal.0c03334article-commentaryACS PublicationsCopyright © 2020 American Chemical Society. This publication is available under these Terms Use. Request reuse permissions free to access through this site. Learn MoreArticle Views15643Altmetric-Citations116LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum full text article downloads since November 2008 (both PDF HTML) across all institutions individuals. These metrics regularly updated reflect usage leading up last few days.Citations number other articles citing article, calculated Crossref daily. Find more information about citation counts.The Altmetric Attention Score a quantitative measure attention that research has received online. Clicking on donut icon will load page at altmetric.com with additional details score social media presence for given article. how calculated. Share Add toView InAdd Full Text ReferenceAdd Description ExportRISCitationCitation abstractCitation referencesMore Options onFacebookTwitterWechatLinked InRedditEmail (3 MB) Get e-AlertscloseSUBJECTS:Alkyls,Amides,Coupling reactions,Cross coupling reaction,Organic compounds e-Alerts

Language: Английский

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Highly selective synthesis of all-carbon tetrasubstituted alkenes by deoxygenative alkenylation of carboxylic acids

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Feb. 4, 2022

Abstract The synthesis of all-carbon tetrasubstituted olefins under mild reaction conditions is challenging because the inevitable issues including significant steric hindrance and uncontrolled Z/E stereoselectivity. In this paper, we report alkenes from readily available carboxylic acids alkenyl triflates with synergistic catalysis cyclo-octa-1,5-diene(tetramethyl-1,4-benzoquinone)nickel visible light an air atmosphere, thus avoiding need for a glovebox or Schlenk line. A wide range aromatic cyclic acyclic undergo C-C coupling process smoothly, forming structurally diverse stereospecifically in moderate to good yields. practicality method further illustrated by late-stage modification complex molecules, one pot gram-scale applications. This important step towards valuable utilization acids, it also simplifies experimental operation metallophotoredox moisture sensitive nickel(0) catalysis.

Language: Английский

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Photocatalytic furan-to-pyrrole conversion

Science, Journal Year: 2024, Volume and Issue: 386(6717), P. 99 - 105

Published: Oct. 3, 2024

The identity of a heteroatom within an aromatic ring influences the chemical properties that heterocyclic compound. Systematically evaluating effect single atom, however, poses synthetic challenges, primarily as result thermodynamic mismatches in atomic exchange processes. We present photocatalytic strategy swaps oxygen atom furan with nitrogen group, directly converting into pyrrole analog intermolecular reaction. High compatibility was observed various derivatives and nucleophiles commonly used drug discovery, late-stage functionalization furnished otherwise difficult-to-access pyrroles from naturally occurring furans high molecular complexity. Mechanistic analysis suggested polarity inversion through electron transfer initiates redox-neutral processes at room temperature.

Language: Английский

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Nickel-Catalyzed Enantioselective Carbamoyl Iodination: A Surrogate for Carbamoyl Iodides

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(8), P. 4780 - 4785

Published: March 26, 2020

This work reports the enantioselective formal transfer of a carbamoyl iodide across 1,1-disubstituted styrene using Ni-catalysis. Employing an air-stable Ni(II) precatalyst and commercially available chiral ligand ((S)-tBuPHOX), enantioenriched 3,3-disubstituted iodooxindoles were obtained in up to 90% yield 97:3 e.r. methodology was applied total synthesis (−)-esermethole (−)-phenserine.

Language: Английский

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Structure–Reactivity Relationships of Buchwald-Type Phosphines in Nickel-Catalyzed Cross-Couplings

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(42), P. 19635 - 19648

Published: Oct. 17, 2022

The dialkyl-ortho-biaryl class of phosphines, commonly known as Buchwald-type ligands, are among the most important phosphines in Pd-catalyzed cross-coupling. These ligands have also been successfully applied to several synthetically valuable Ni-catalyzed cross-coupling methodologies and, demonstrated this work, top performing Suzuki Miyaura Coupling (SMC) and C-N coupling reactions, even outperforming employed bisphosphines like dppf many circumstances. However, little is about their structure-reactivity relationships (SRRs) with Ni, limited examples well-defined, catalytically relevant Ni complexes exist. In we report analysis phosphine SRRs four representative reactions. Our study was guided by data-driven classification analysis, which together mechanistic organometallic studies structurally characterized Ni(0), Ni(I), Ni(II) allowed us rationalize reactivity patterns catalysis. Overall, expect that will serve a platform for further exploration ligand organonickel chemistry well development new methodologies.

Language: Английский

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Collaboration as a Key to Advance Capabilities for Earth-Abundant Metal Catalysis

Organic Process Research & Development, Journal Year: 2023, Volume and Issue: 27(7), P. 1160 - 1184

Published: March 20, 2023

Earth-abundant metal (EAM) catalysis can have profound impact in the pharmaceutical industry terms of sustainability and cost improvements from replacing precious metals like palladium as well harnessing differential reactivity first-row that allows for novel transformations to enable more efficient routes clinical candidates. The strategy building these capabilities within process group at Bristol Myers Squibb is described herein, with general plan a reaction screening platform, demonstrating scalability, increasing mechanistic understanding catalyst activation. development catalytic utilizing nickel, cobalt, iron while highlighting importance collaboration internal external groups advance EAM our portfolio. challenges benefits working transition metals, including metrics implementation catalysis, such cost, mass intensity, commercial availability catalysts ligands, are discussed.

Language: Английский

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Selective C(aryl)–O bond cleavage in biorenewable phenolics

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(11), P. 5489 - 5551

Published: Jan. 1, 2024

Selective removal of the hydroxy, methoxy or both groups in biorenewable oxygenated arenes (derived from lignin depolymerization) provides, respectively, anisoles, phenols and benzenes.

Language: Английский

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Rational design of new in situ reduction of Ni(II) catalytic system for low‐cost and large‐scale preparation of porous aromatic frameworks

Carbon Energy, Journal Year: 2024, Volume and Issue: 6(5)

Published: Jan. 9, 2024

Abstract Porous aromatic framework 1 (PAF‐1) is an extremely representative nanoporous organic owing to its high stability and exceptionally surface area. Currently, the synthesis of PAF‐1 catalyzed by Ni(COD) 2 /COD/bpy system, suffering from great instability cost. Herein, we developed in situ reduction Ni(II) catalytic system synthesize low cost yield. The active Ni(0) species produced NiCl /bpy/NaI/Mg catalyst can effectively catalyze homocoupling tetrakis(4‐bromophenyl)methane at room temperature form with Brunauer–Emmett–Teller (BET)‐specific area up 4948 m g −1 (Langmuir area, 6785 ). possible halogen exchange dehalogenation coupling mechanisms for this new process PAF's are discussed detail. efficiency universality innovative have also been demonstrated other PAFs' synthesis. This work provides a cheap, facile, efficient method scalable PAFs explores their application high‐pressure storage Xe Kr.

Language: Английский

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MAdPHOS, a P-Stereogenic Aminodiphosphane Ligand with Adamantyl Groups: Synthesis, NH/PH Tautomerism, and Rhodium and Nickel Complexes

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 28, 2025

A novel chiral ligand, named MAdPHOS, bearing a P-stereogenic phosphane and diadamantyl linked by NH bridge has been synthesized. This bulky, C1-symmetric, PNP ligand prepared from enantiopure tert-butylmethyl aminophosphane was obtained as crystalline solid. The NH/PH tautomerism, air-stability, σ-donor capacity of MAdPHOS have assessed herein. free prepared, showing much higher stability, in the solid form, than its tert-butyl analogue MaxPHOS. Both rhodium nickel COD complexes prepared. Rh-MAdPHOS complex shown outstanding enantioselectivities asymmetric hydrogenation enamides.

Language: Английский

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