Metal-organic framework (MOF) nanoparticles, also called porous coordination polymers, are a major part of nanomaterials science, and their role in catalysis is becoming central. The extraordinary variability and richness of their structures afford engineering synergies between the metal nodes, functional linkers, encapsulated substrates, or nanoparticles for multiple and selective heterogeneous interactions and activations in these MOF-based nanocatalysts. Pyrolysis of MOF-nanoparticle composites forms highly porous N- or P-doped graphitized MOF-derived nanomaterials that are increasingly used as efficient catalysts especially in electro- and photocatalysis. This review first briefly summarizes this background of MOF nanoparticle catalysis and then comprehensively reviews the fast-growing literature reported during the last years. The major parts are catalysis of organic and molecular reactions, electrocatalysis, photocatalysis, and views of prospects. Major challenges of our society are addressed using these well-defined heterogeneous catalysts in the fields of synthesis, energy, and environment. In spite of the many achievements, enormous progress is still necessary to improve our understanding of the processes involved beyond the proof-of-concept, particularly for selective methane oxidation, hydrogen production, water splitting, CO2 reduction to methanol, nitrogen fixation, and water depollution.

State of the Art and Prospects in Metal-Organic Framework (MOF)-Based and MOF-Derived Nanocatalysis.

Organosulfur compounds have long played a vital role in organic chemistry and in the development of novel chemical structures and architectures. Prominent among these organosulfur compounds are those involving a sulfur(IV) center, which have been the subject of countless investigations over more than a hundred years. In addition to a long list of textbook sulfur-based reactions, there has been a sustained interest in the chemistry of organosulfur(IV) compounds in recent years. Of particular interest within organosulfur chemistry is the ease with which the synthetic chemist can effect a wide range of transformations through either bond formation or bond cleavage at sulfur. This review aims to cover the developments of the past decade in the chemistry of organic sulfur(IV) molecules and provide insight into both the wide range of reactions which critically rely on this versatile element and the diverse scaffolds that can thereby be synthesized.

Bond-Forming and -Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur Ylides, and Sulfinate Salts.

Advanced Organic Chemistry: Reactions, Mechanisms And Structure

A method for the efficient enantioselective oxytrifluoromethylation of alkenes has been developed using a copper catalyst system. Mechanistic studies are consistent with a metal-catalyzed redox radical addition mechanism, in which a C–O bond is formed via the copper-mediated enantioselective trapping of a prochiral alkyl radical intermediate derived from the initial trifluoromethyl radical addition.

Enantioselective Functionalization of Radical Intermediates in Redox Catalysis: Copper-Catalyzed Asymmetric Oxytrifluoromethylation of Alkenes

The ever increasing industrial production of commodity and specialty chemicals inexorably depletes the finite primary fossil resources available on Earth. The forecast of population growth over the next 3 decades is a very strong incentive for the identification of alternative primary resources other than petro-based ones. In contrast with fossil resources, renewable biomass is a virtually inexhaustible reservoir of chemical building blocks. Shifting the current industrial paradigm from almost exclusively petro-based resources to alternative bio-based raw materials requires more than vibrant political messages; it requires a profound revision of the concepts and technologies on which industrial chemical processes rely. Only a small fraction of molecules extracted from biomass bears significant chemical and commercial potentials to be considered as ubiquitous chemical platforms upon which a new, bio-based industry can thrive. Owing to its inherent assets in terms of unique process experience, scalability, and reduced environmental footprint, flow chemistry arguably has a major role to play in this context. This review covers a selection of C2 to C6 bio-based chemical platforms with existing commercial markets including polyols (ethylene glycol, 1,2-propanediol, 1,3-propanediol, glycerol, 1,4-butanediol, xylitol, and sorbitol), furanoids (furfural and 5-hydroxymethylfurfural) and carboxylic acids (lactic acid, succinic acid, fumaric acid, malic acid, itaconic acid, and levulinic acid). The aim of this review is to illustrate the various aspects of upgrading bio-based platform molecules toward commodity or specialty chemicals using new process concepts that fall under the umbrella of continuous flow technology and that could change the future perspectives of biorefineries.

Continuous Flow Upgrading of Selected C2-C6 Platform Chemicals Derived from Biomass.

Direct C−H Trifluoromethylation of Quinoxalin‐2(1H)‐ones under Transition‐Metal‐Free Conditions

A 3.1% Ru/UiO-66 material was prepared by adsorption of RuCl3 from ethyl acetate on to MOF UiO-66, followed by reduction with NaBH4. The presence of acid–base and ox-red sites allows this 3.1% Ru/UiO-66 material acting as a bifunctional catalyst for the reduction of nitroarenes and tandem reaction of alcohol oxidation/Knoevenagel condensation. The high efficiency of 3.1% Ru/UiO-66 was demonstrated in the reduction of nitroarenes to amines. This system can be applied as a catalyst for at least six successive cycles without loss of activity. The 3.1% Ru/UiO-66 catalyst also was active in the tandem aerobic oxidation of alcohols/Knoevenagel condensation with malononitrile. However, the activity of this catalyst strongly decreased in the second cycle. A combination of physicochemical and catalytic experimental data indicated that Ru nanoparticles are the active sites both for the catalytic reduction of nitro compounds and the aerobic oxidation of alcohols. The activity for the Knoevenagel condensation reactio...

Hong-Yu Zhang

Papers

Direct C−H Trifluoromethylation of Quinoxalin‐2(1H)‐ones under Transition‐Metal‐Free Conditions

Ru/UiO-66 Catalyst for the Reduction of Nitroarenes and Tandem Reaction of Alcohol Oxidation/Knoevenagel Condensation

Copper-Catalyzed C3−H Difluoroacetylation of Quinoxalinones with Ethyl Bromodifluoroacetate

Cobalt-Catalyzed Trifluoromethylation–Peroxidation of Unactivated Alkenes with Sodium Trifluoromethanesulfinate and Hydroperoxide

Direct C(sp2)−H Amination to Synthesize Primary 3-aminoquinoxalin-2(1H)-ones under Simple and Mild Conditions