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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3d Transition Metals for C–H Activation

Chemical Reviews, Journal Year: 2018, Volume and Issue: 119(4), P. 2192 - 2452

Published: Nov. 27, 2018

C–H activation has surfaced as an increasingly powerful tool for molecular sciences, with notable applications to material crop protection, drug discovery, and pharmaceutical industries, among others. Despite major advances, the vast majority of these functionalizations required precious 4d or 5d transition metal catalysts. Given cost-effective sustainable nature earth-abundant first row metals, development less toxic, inexpensive 3d catalysts gained considerable recent momentum a significantly more environmentally-benign economically-attractive alternative. Herein, we provide comprehensive overview on until summer 2018.

Language: Английский

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A comprehensive overview of directing groups applied in metal-catalysed C–H functionalisation chemistry

Chemical Society Reviews, Journal Year: 2018, Volume and Issue: 47(17), P. 6603 - 6743

Published: Jan. 1, 2018

The present review is devoted to summarizing the recent advances (2015-2017) in field of metal-catalysed group-directed C-H functionalisation. In order clearly showcase molecular diversity that can now be accessed by means directed functionalisation, whole organized following directing groups installed on a substrate. Its aim comprehensive reference work, where specific group easily found, together with transformations which have been carried out it. Hence, primary format this schemes accompanied concise explanatory text, are ordered sections according their chemical structure. feature typical substrates used, products obtained as well required reaction conditions. Importantly, each example commented respect most important positive features and drawbacks, aspects such selectivity, substrate scope, conditions, removal, greenness. targeted readership both experts functionalisation chemistry (to provide overview progress made last years) and, even more so, all organic chemists who want introduce way thinking for design straightforward, efficient step-economic synthetic routes towards molecules interest them. Accordingly, should particular also scientists from industrial R&D sector. overall goal promote application reactions outside research dedicated method development establishing it valuable archetype contemporary R&D, comparable role cross-coupling play date.

Language: Английский

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C–H Activation: Toward Sustainability and Applications

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(2), P. 245 - 261

Published: Feb. 2, 2021

Since the definition of "12 Principles Green Chemistry" more than 20 years ago, chemists have become increasingly mindful need to conserve natural resources and protect environment through judicious choice synthetic routes materials. The direct activation functionalization C–H bonds, bypassing intermediate functional group installation is, in abstracto, step atom economic, but numerous factors still hinder sustainability large-scale applications. In this Outlook, we highlight research areas seeking overcome challenges activation: pursuit abundant metal catalysts, avoidance static directing groups, replacement oxidants, introduction bioderived solvents. We close by examining progress made subfield aryl borylation from its origins, highly efficient precious Ir-based systems, emerging 3d catalysts. future growth field will depend on industrial uptake, thus urge researchers strive toward sustainable activation.

Language: Английский

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Manganese-Catalyzed C–H Activation

ACS Catalysis, Journal Year: 2016, Volume and Issue: 6(6), P. 3743 - 3752

Published: April 27, 2016

Manganese is found in the active center of numerous enzymes that operate by an outer-sphere homolytic C–H cleavage. Thus, a plethora bioinspired radical-based functionalizations manganese catalysis have been devised during past decades. In contrast, organometallic activation means has emerged only recently as increasingly viable tool organic synthesis. These manganese(I)-catalyzed processes enabled variety with ample scope, which very set stage for substitutive functionalizations. The versatile largely operates isohypsic, thus redox-neutral, mode action through chelation assistance, and provided step-economical access to structurally divers compounds relevance inter alia bioorganic, agrochemical, medicinal chemistry well material sciences.

Language: Английский

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C–H activation

Nature Reviews Methods Primers, Journal Year: 2021, Volume and Issue: 1(1)

Published: June 17, 2021

Language: Английский

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Recent advances in positional-selective alkenylations: removable guidance for twofold C–H activation

Organic Chemistry Frontiers, Journal Year: 2017, Volume and Issue: 4(7), P. 1435 - 1467

Published: Jan. 1, 2017

Recent advances in transition-metal catalyzed positional-selective alkenylations via twofold C–H activation directed by removable or traceless directing groups are reviewed.

Language: Английский

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Green Chemistry in the Synthesis of Pharmaceuticals

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(3), P. 3637 - 3710

Published: Dec. 15, 2021

The principles of green chemistry (GC) can be comprehensively implemented in synthesis pharmaceuticals by choosing no solvents or (preferably water), alternative reaction media, and consideration one-pot synthesis, multicomponent reactions (MCRs), continuous processing, process intensification approaches for atom economy final waste reduction. GC's execution performed using a holistic design the active pharmaceutical ingredient's (API) life cycle, minimizing hazards pollution, capitalizing resource efficiency technique. Thus, presented review accounts comprehensive exploration metrics, an appropriate implication those ideas each step schemes, from raw material to intermediate product's into scalable industry-based production. For real-life examples, we have discussed series established generic pharmaceuticals, starting with materials, intermediates corresponding pharmaceuticals. Researchers industries thoughtfully instigated control reduction protect environment. We extensively significant relevant cascade MCRs, intensification, which may contribute future sustainable APIs.

Language: Английский

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Control Interlayer Stacking and Chemical Stability of Two-Dimensional Covalent Organic Frameworks via Steric Tuning

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(47), P. 16124 - 16133

Published: Nov. 3, 2018

Layer stacking and chemical stability are crucial for two-dimensional covalent organic frameworks (2D COFs), but yet challenging to gain control. In this work, we demonstrate synthetic control of both the layer 2D COFs by managing interlayer steric hindrance via a multivariate (MTV) approach. By co-condensation triamines with without alkyl substituents (ethyl isopropyl) di- or trialdehyde, family two-, three-, four-component AA, AB, ABC is prepared. The groups periodically appended on channel walls their contents, which can be synthetically tuned MTV strategy, model maximizing total crystal energy protecting hydrolytically susceptible backbones through kinetic blocking. Specifically, higher concentration adopt AB stacking, while lower amount functionalities leads AA stacking. bearing high isopropyl represent first identified that retain crystallinity porosity in boiling 20 M NaOH solution. After postsynthetic metalation an iridium complex, 2,2'-bipyridyl-derived heterogeneously catalyze C-H borylation arenes, whereas COF exhibits much activity than ethyl nonsubstituents due increased stability. This work underscores opportunity using tune properties COFs.

Language: Английский

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First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(21), P. 13238 - 13341

Published: Oct. 7, 2021

Organoboron reagents represent a unique class of compounds because their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation the carbon–boron bond into carbon–X (X = C, N, and O) stereocontrolled fashion has become invaluable medicinal agrochemistry, natural products chemistry as well materials science. Over past decade, first-row d-block transition metals have increasingly widely used catalysts for formation bond, traditionally catalyzed by expensive precious metals. This recent focus on alternative enabled growth fundamental methods organoboron chemistry. review surveys current state-of-the-art use element-based bonds.

Language: Английский

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