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

Chemical Reviews, Год журнала: 2018, Номер 118(10), С. 4981 - 5079

Опубликована: Апрель 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.

Язык: Английский

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Applications of Palladium-Catalyzed C–N Cross-Coupling Reactions

Chemical Reviews, Год журнала: 2016, Номер 116(19), С. 12564 - 12649

Опубликована: Сен. 30, 2016

Pd-catalyzed cross-coupling reactions that form C–N bonds have become useful methods to synthesize anilines and aniline derivatives, an important class of compounds throughout chemical research. A key factor in the widespread adoption these has been continued development reliable versatile catalysts function under operationally simple, user-friendly conditions. This review provides overview N-arylation found both basic applied research from 2008 present. Selected examples between nine classes nitrogen-based coupling partners (pseudo)aryl halides are described for synthesis heterocycles, medicinally relevant compounds, natural products, organic materials, catalysts.

Язык: Английский

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Balancing volumetric and gravimetric uptake in highly porous materials for clean energy

Science, Год журнала: 2020, Номер 368(6488), С. 297 - 303

Опубликована: Апрель 16, 2020

A huge challenge facing scientists is the development of adsorbent materials that exhibit ultrahigh porosity but maintain balance between gravimetric and volumetric surface areas for onboard storage hydrogen methane gas-alternatives to conventional fossil fuels. Here we report simulation-motivated synthesis ultraporous metal-organic frameworks (MOFs) based on metal trinuclear clusters, namely, NU-1501-M (M = Al or Fe). Relative other MOFs, NU-1501-Al exhibits concurrently a high Brunauer-Emmett-Teller (BET) area 7310 m2 g-1 BET 2060 cm-3 while satisfying four consistency criteria. The this MOF yielded impressive performances methane: surpasses U.S. Department Energy target (0.5 g g-1) with an uptake 0.66 [262 cm3 (standard temperature pressure, STP) cm-3] at 100 bar/270 K 5- 100-bar working capacity 0.60 [238 (STP) 270 K; it also shows one best deliverable capacities (14.0 weight %, 46.2 liter-1) under combined pressure swing (77 K/100 bar → 160 K/5 bar).

Язык: Английский

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Selected Copper‐Based Reactions for C−N, C−O, C−S, and C−C Bond Formation

Angewandte Chemie International Edition, Год журнала: 2017, Номер 56(51), С. 16136 - 16179

Опубликована: Май 23, 2017

Abstract Metal‐catalyzed cross‐coupling reactions belong to the most important transformations in organic synthesis. Copper catalysis has received great attention owing low toxicity and cost of copper. However, traditional Ullmann‐type couplings suffer from limited substrate scopes harsh reaction conditions. The introduction several bidentate ligands, such as amino acids, diamines, 1,3‐diketones, oxalic diamides, over past two decades totally changed this situation these ligands enable copper‐catalyzed coupling aryl halides nucleophiles at both temperatures catalyst loadings. scope also been greatly expanded, rendering copper‐based attractive for academia industry. In Review, we have summarized latest progress development useful conditions (hetero)aryl with different nucleophiles. Additionally, recent advances boronates trifluoromethylation aromatic electrophiles will be discussed.

Язык: Английский

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Nanomole-scale high-throughput chemistry for the synthesis of complex molecules

Science, Год журнала: 2014, Номер 347(6217), С. 49 - 53

Опубликована: Ноя. 21, 2014

Breaking through the milligram floor When chemists synthesize compounds, threshold for success is at least a of product. This has been true decades—even though biochemical assays have long since descended into microgram territory—and results in part from constraints characterization methods. Buitrago Santanilla et al. present an automated dosing and protocol optimizing chemical reaction conditions on scale. allowed them to screen numerous base ligand combinations catalytic C-N bond-forming reactions between complex pairs short supply, that resisted standard coupling conditions. Science , this issue p. 49

Язык: Английский

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Prediction of higher-selectivity catalysts by computer-driven workflow and machine learning

Science, Год журнала: 2019, Номер 363(6424)

Опубликована: Янв. 18, 2019

Catalyst design in asymmetric reaction development has traditionally been driven by empiricism, wherein experimentalists attempt to qualitatively recognize structural patterns improve selectivity. Machine learning algorithms and chemoinformatics can potentially accelerate this process recognizing otherwise inscrutable large datasets. Herein we report a computationally guided workflow for chiral catalyst selection using at every stage of development. Robust molecular descriptors that are agnostic the scaffold allow universal training set on basis steric electronic properties. This be used train machine methods make highly accurate predictive models over broad range selectivity space. Using support vector machines deep feed-forward neural networks, demonstrate modeling phosphoric acid-catalyzed thiol addition N-acylimines.

Язык: Английский

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The Evolution of High-Throughput Experimentation in Pharmaceutical Development and Perspectives on the Future

Organic Process Research & Development, Год журнала: 2019, Номер 23(6), С. 1213 - 1242

Опубликована: Май 7, 2019

High-throughput experimentation (HTE) has revolutionized the pharmaceutical industry, most notably allowing for rapid screening of compound libraries against therapeutic targets. The past decade also witnessed extension HTE principles toward realm small-molecule process chemistry. Today, major companies have created dedicated groups within their development teams, invested in automation technology to accelerate screening, or both. industry's commitment accelerating led innovations space. This review will deliver an overview latest best practices currently taking place our teams chemistry by sharing frequently studied transformations, perspective next several years field, and manual automated tools enable experimentation. A series case studies are presented exemplify state-of-the-art workflows developed laboratories.

Язык: Английский

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Reconfigurable system for automated optimization of diverse chemical reactions

Science, Год журнала: 2018, Номер 361(6408), С. 1220 - 1225

Опубликована: Сен. 20, 2018

Chemical synthesis generally requires labor-intensive, sometimes tedious trial-and-error optimization of reaction conditions. Here, we describe a plug-and-play, continuous-flow chemical system that mitigates this challenge with an integrated combination hardware, software, and analytics. The software controls the user-selected reagents unit operations (reactors separators), processes analytics (high-performance liquid chromatography, mass spectrometry, vibrational spectroscopy), conducts automated optimizations. capabilities are demonstrated in high-yielding implementations C-C C-N cross-coupling, olefination, reductive amination, nucleophilic aromatic substitution (SNAr), photoredox catalysis, multistep sequence. graphical user interface enables users to initiate optimizations, monitor progress remotely, analyze results. Subsequent optimized procedure need only download electronic file, comparable smartphone application, implement protocol on their own apparatus.

Язык: Английский

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Well-defined nickel and palladium precatalysts for cross-coupling

Nature Reviews Chemistry, Год журнала: 2017, Номер 1(3)

Опубликована: Март 1, 2017

Язык: Английский

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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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