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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Transition metal-catalysis in interrupted borrowing hydrogen strategy

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(51), P. 7847 - 7862

Published: Jan. 1, 2023

This review article highlights the recent advances of transition-metal-catalyzed interrupted borrowing hydrogen (IBH) catalysis and its applications in sustainable affordable chemical synthesis using alcohols as C1 feedstocks.

Language: Английский

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Dehydrogenative Synthesis of Quinolines and Quinazolines via Ligand-Free Cobalt-Catalyzed Cyclization of 2-Aminoaryl Alcohols with Ketones or Nitriles

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(19), P. 12596 - 12607

Published: Sept. 26, 2022

We present a convenient and efficient protocol to synthesize quinolines quinazolines in one pot under mild conditions. A variety of substituted were synthesized good excellent yields (up 97% yield) from the dehydrogenative cyclizations 2-aminoaryl alcohols ketones catalyzed by readily available Co(OAc)2·4H2O. This cobalt catalytic system also showed high activity reactions 2-aminobenzyl with nitriles, affording various quinazoline derivatives 95% yield). The offers an environmentally benign approach for synthesis N-heterocycles employing earth-abundant salt ligand-free

Language: Английский

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Complexation of guanidino containing l-arginine with nickel on silica-modified Hercynite MNPs: a novel catalyst for the Hantzsch synthesis of polyhydroquinolines and 2,3-Dihydroquinazolin-4(1H)-ones

Research on Chemical Intermediates, Journal Year: 2022, Volume and Issue: 48(6), P. 2641 - 2663

Published: April 5, 2022

Language: Английский

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Ruthenium pincer complex catalyzed efficient synthesis of quinoline, 2-styrylquinoline and quinazoline derivatives via acceptorless dehydrogenative coupling reactions

Catalysis Science & Technology, Journal Year: 2022, Volume and Issue: 12(18), P. 5695 - 5702

Published: Jan. 1, 2022

The synthesis of N-heterocycles has been considered an emerging area chemical research due to their extensive utilization in pharmaceuticals, materials science, and natural product synthesis.

Language: Английский

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First‐Row Transition‐Metal Catalyzed Acceptorless Dehydrogenation and Related Reactions: A Personal Account

The Chemical Record, Journal Year: 2021, Volume and Issue: 21(12), P. 3839 - 3871

Published: Aug. 20, 2021

Abstract The development of sustainable catalytic protocols that circumvent the use expensive and precious metal catalysts avoid toxic reagents plays a crucial role in organic synthesis. Indeed, direct employment simple abundantly available feedstock chemicals as starting materials broadens their synthetic application contemporary research. In particular, transition metal‐catalyzed diversification alcohols with various nucleophilic partners to construct wide range building blocks is powerful highly desirable methodology. Moreover, replacement by non‐precious less metals for selective transformations one main goals has been paid significant attention modern chemistry. view this, first‐row find extensive applications such hydrogenation, dehydrogenation, related reactions. Herein, we have disclosed our recent developments on base‐metal catalysis Mn, Fe, Co, Ni acceptorless dehydrogenation reactions its C−C C−N bond formation via hydrogen auto‐transfer (HA) coupling (ADC) These HA/ADC employ alcohol alkylating agents eliminate water and/or gas by‐products, representing atom‐efficient environmentally benign Furthermore, diverse complex molecules synthesis using are also overviewed. Overall, this account deals contribution efficient novel homogeneous well heterogeneous chemical

Language: Английский

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Cobalt-catalysed CH-alkylation of indoles with alcohols by borrowing hydrogen methodology

Green Chemistry, Journal Year: 2022, Volume and Issue: 24(11), P. 4566 - 4572

Published: Jan. 1, 2022

A general heterogeneous cobalt-catalysed CH-alkylation of indoles with alcohols is reported.

Language: Английский

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Well‐Defined Ni−SNS Complex Catalysed Borrowing Hydrogenative α‐Alkylation of Ketones and Dehydrogenative Synthesis of Quinolines

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(14), P. 2429 - 2437

Published: May 23, 2022

Abstract The “borrowing hydrogen” (BH) method for C‐alkylation reactions using alcohol as alkylating agents is an important synthetic transformation. In this respect, designing cheap and bench stable earth abundant metal catalyst borrowing hydrogen transformation a key challenge to be witnessed. Herein we have presented synthesis of non‐phosphine, easily accessible SNS−Ni complexes. Ni‐catalyst was successfully applied the ketone enolates α‐alkylated ketones. Primary with different functional groups various heteroaromatic alcohols are well tolerated. present system efficiently gram scale also green chemistry metrics reaction were calculated. protocol extended biologically quinoline moieties. Finally, control experiments deuterium labelled suggest that proceeds via pathway. magnified image

Language: Английский

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A sustainable approach for nickel nanoparticles synthesis: expeditious access to N-heterocycles under heterogeneous condition and photophysical studies

New Journal of Chemistry, Journal Year: 2023, Volume and Issue: 47(17), P. 8268 - 8276

Published: Jan. 1, 2023

A sustainable and environmentally benign biogenic technique for one-step synthesis of Ni-NPs (NiC 2 O 4 ·2H O-NPs) using Portulaca oleracea (purslane) leaf extract has been disclosed the first time.

Language: Английский

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Nickel catalyzed sustainable synthesis of benzazoles and purines via acceptorless dehydrogenative coupling and borrowing hydrogen approach

Organic & Biomolecular Chemistry, Journal Year: 2021, Volume and Issue: 19(33), P. 7217 - 7233

Published: Jan. 1, 2021

Herein we report nickel-catalyzed sustainable synthesis of a few chosen five-membered fused nitrogen heterocycles such as benzimidazole, purine, benzothiazole, and benzoxazole via acceptorless dehydrogenative functionalization alcohols. Using bench stable, easy to prepare, inexpensive Ni(ii)-catalyst, [Ni(MeTAA)] (1a), featuring tetraaza macrocyclic ligand (tetramethyltetraaza[14]annulene (MeTAA)), wide variety polysubstituted derivatives were prepared coupling alcohols with 1,2-diaminobenzene, 4,5-diaminopyrimidine, 2-aminothiphenol, 2-aminophenol, respectively. A array benzimidazoles also borrowing hydrogen approach involving donors 2-nitroanilines acceptors. control experiments performed understand the reaction mechanism.

Language: Английский

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