Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles

Chemical Reviews, Journal Year: 2018, Volume and Issue: 118(10), P. 4981 - 5079

Published: April 16, 2018

Metal species with different size (single atoms, nanoclusters, and nanoparticles) show catalytic behavior for various heterogeneous reactions. It has been shown in the literature that many factors including particle size, shape, chemical composition, metal–support interaction, metal–reactant/solvent interaction can have significant influences on properties of metal catalysts. The recent developments well-controlled synthesis methodologies advanced characterization tools allow one to correlate relationships at molecular level. In this Review, electronic geometric structures single nanoparticles will be discussed. Furthermore, we summarize applications types reactions, CO oxidation, selective hydrogenation, organic electrocatalytic, photocatalytic We compare results obtained from systems try give a picture how work reactions perspectives future directions toward better understanding entities unifying manner.

Language: Английский

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Electrocatalytic C–H Activation

ACS Catalysis, Journal Year: 2018, Volume and Issue: 8(8), P. 7086 - 7103

Published: June 18, 2018

C–H activation has emerged as a transformative tool in molecular synthesis, but until recently oxidative activations have largely involved the use of stoichiometric amounts expensive and toxic metal oxidants, compromising overall sustainable nature chemistry. In sharp contrast, electrochemical been identified more efficient strategy that exploits storable electricity place byproduct-generating chemical reagents. Thus, transition-metal catalysts were shown to enable versatile reactions manner. While palladium catalysis set stage for C(sp2)–H C(sp3)–H functionalizations by N-containing directing groups, rhodium ruthenium allowed weakly coordinating amides acids. contrast these precious 4d transition metals, recent year witnessed emergence cobalt oxygenations, nitrogenations, C–C-forming [4+2] alkyne annulations. Thereby, silver(I) oxidants was prevented, improving environmentally benign catalysis. Herein, we summarize major advances organometallic otherwise inert bonds electrocatalysis through May 2018.

Language: Английский

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Transient Directing Groups for Transformative C–H Activation by Synergistic Metal Catalysis

Chem, Journal Year: 2017, Volume and Issue: 4(2), P. 199 - 222

Published: Dec. 21, 2017

Language: Английский

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Transition metal-catalyzed site- and regio-divergent C–H bond functionalization

Chemical Society Reviews, Journal Year: 2017, Volume and Issue: 46(14), P. 4299 - 4328

Published: Jan. 1, 2017

The regioselectivity of C–H functionalization reactions can be redirected to obtain regioisomeric products form the same starting materials.

Language: Английский

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Beyond C2 and C3: Transition-Metal-Catalyzed C–H Functionalization of Indole

ACS Catalysis, Journal Year: 2017, Volume and Issue: 7(9), P. 5618 - 5627

Published: July 11, 2017

The indole scaffold will continue to play a vital part in the future of drug discovery and agrochemical development. Because this, necessity for elegant techniques enable selective C–H functionalization is vast. Early developments have led primarily C2 C3 because inherent reactivity pyrrole ring. Despite methods been developed on benzenoid moiety at C4, C5, C6, C7. This review focuses contributions made indoles other related heteroaromatics such as carbazoles.

Language: Английский

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Toolbox for Distal C–H Bond Functionalizations in Organic Molecules

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(6), P. 5682 - 5841

Published: Oct. 18, 2021

Transition-metal-catalyzed C–H activation has developed a contemporary approach to the omnipresent area of retrosynthetic disconnection. Scientific researchers have been tempted take help this methodology plan their synthetic discourses. This paradigm shift helped in development industrial units as well, making synthesis natural products and pharmaceutical drugs step-economical. In vast zone bond activation, functionalization proximal bonds gained utmost popularity. Unlike bonds, distal is more strenuous requires distinctly specialized techniques. review, we compiled various methods adopted functionalize mechanistic insights within each these procedures, scope methodology. With give complete overview expeditious progress made field organic chemistry while also highlighting its pitfalls, thus leaving open for further modifications.

Language: Английский

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Ruthenium-catalysed σ-activation for remote meta-selective C–H functionalisation

Chemical Society Reviews, Journal Year: 2017, Volume and Issue: 46(23), P. 7145 - 7153

Published: Jan. 1, 2017

The search for selective C-H functionalisation has enabled some of the most elegant techniques in modern catalysis. Herein, we review rapidly expanding field ruthenium catalysed σ-activation as a tool meta-C-H arenes.

Language: Английский

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Advances on the Merger of Electrochemistry and Transition Metal Catalysis for Organic Synthesis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(3), P. 3180 - 3218

Published: Nov. 19, 2021

Synthetic organic electrosynthesis has grown in the past few decades by achieving many valuable transformations for synthetic chemists. Although electrocatalysis been popular improving selectivity and efficiency a wide variety of energy-related applications, last two decades, there much interest to develop conceptually novel transformations, selective functionalization, sustainable reactions. This review discusses recent advances combination electrochemistry homogeneous transition-metal catalysis synthesis. The enabling mechanistic studies are presented alongside advantages as well future directions address challenges metal-catalyzed electrosynthesis.

Language: Английский

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Mechanistic view of Ru-catalyzed C–H bond activation and functionalization: computational advances

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(20), P. 7552 - 7576

Published: Jan. 1, 2018

Ru-Catalyzed aromatic C-H bond activation and functionalization have emerged as important topics because they resulted in remarkable progress organic synthesis. Both experimental theoretical studies of their mechanisms are for the design new synthetic methodologies. In this review, a mechanistic view Ru-mediated cleavage step is first given to reveal modes, including oxidative addition, metathesis base-assisted deprotonation. process, directing groups play an role determining reactivity bond. The generally leads formation Ru-C bond, which further functionalized subsequent steps. Ru-catalyzed arylation, alkylation, alkenylation arenes summarized, these transformations can be categorized into cross-coupling with electrophiles or coupling nucleophiles. mechanism ortho-ruthenation-enabled remote also discussed.

Language: Английский

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Access to the meta position of arenes through transition metal catalysed C–H bond functionalisation: a focus on metals other than palladium

Chemical Society Reviews, Journal Year: 2017, Volume and Issue: 47(1), P. 149 - 171

Published: Oct. 26, 2017

The elaboration of simple arenes in order to access more complex substitution patterns is a crucial endeavor for synthetic chemists, given the central role that aromatic rings play all manner important molecules. Classical methods are now routinely used alongside stoichiometric organometallic approaches and, most recently, transition metal catalysis range methodologies available elaborate arene C-H bonds. Regioselectivity an consideration when selecting method those available, it arguably target meta position fewest number. rapid development metal-catalysed bond functionalisation over last few decades has opened new possibilities meta-selective through diverse reactivity metals and their compatibility with wide directing groups. pace discovery such processes grown rapidly five years particular purpose this review examine these but doing so place focus on other than palladium, specific contributions which have been very recently reviewed elsewhere. It hoped will serve highlight reader breadth current strategies mechanisms tackle challenge, may inspire further progress field.

Language: Английский

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