Topics in Current Chemistry最新文献

Water collection from moisture in air, i.e., atmospheric water harvesting, is an urgent future need for society. It can be used for water production everywhere and anytime as an alternative water source in remote areas. However, water harvesting and collection usually relies on desalination, fog, and dewing harvesting, which are energy intensive. In this respect, metal–organic frameworks (MOFs) have broad applicability for water harvesting in water-scarce areas; therefore, the current discussion focuses on this approach. Furthermore, recent progress on MOFs for moisture harvesters is critically discussed. In addition, the design, operation, and water harvesting mechanisms of MOFs are studied. Finally, we discuss critical points for future research for the design of new MOFs as moisture harvesters for use in practical applications.

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MOF adsorbents offer excellent operating capacity in various temperature and pressure ranges. Rational water harvesters can thus be developed by adjusting structural properties such as the porosity, functionalities, and metal centers, thereby enabling new devices to produce water even in remote areas.

Reaction rate acceleration using green methods is an intriguing area of research for chemists. In this regard, water as a “green solvent” plays a crucial role in the acceleration of some organic transformations and reveals exclusive selectivity and reactivity in comparison with conventional organic solvents. In particular, multicomponent reactions (MCRs) as sustainable tools lead to the rapid generation of small-molecule libraries in water and aqueous media due to the prominent role of the hydrophobic effect. MCRs, as diversity-oriented synthesis (DOS) methods, have great efficiency with simple operations, atom, pot, and step economy synthesis, and mechanistic beauty. Among diverse classes of MCRs, isocyanide-based multicomponent reactions (I-MCRs), as sustainable and versatile reactions, have gained considerable attention in the synthesis of diverse heterocycle rings, especially in drug design because of the peculiar nature of isocyanide as a particular active reactant. I-MCRs that are performed in water are mild, environmentally friendly, and easily controlled, and have a reduced number of workup, purification, and extraction steps, which fit well with the advantages of “green” chemistry. Performing these powerful organic transformations in water and aqueous media is accompanied by acceleration owing to negative activation volumes, which originate from connecting several reactants together to generate a single product. It should be noted that the combination of MCR strategy and aqueous phase reaction is of growing interest for the development of sustainable synthetic techniques in organic conversions. However, an exclusive account focusing on the recent progress in eco-friendly I-MCRs for the construction of heterocycles in water and aqueous media is particularly lacking. This review highlights the progress of various kinds of I-MCRs in water and aqueous media as benign methods for the efficient construction of vital heterocyclic scaffolds, with a critical discussion of the subject in the period 2000–2021. We hope that this themed collection will be of interest and beneficial for organic and pharmaceutical chemists and will inspire more reaction development in this fascinating field.

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Enantioselective synthesis through photocatalysis is one of the highly preferred approaches towards preparation of optically active compounds. This review elaborates and critically analyzes the different strategies of photocatalytic enantioselective reactions through H-bonding, transition metal catalysis, phase-transfer catalysis (PTC), chiral Lewis acid catalysis, N-heterocyclic carbene catalysis, and amine catalysis, and also explores ion pairs. In addition, it explains the different catalysis modes with multifunctional approaches for enantioselective photocatalytic reactions.

In photocatalysis, a set of elemental steps are involved together at different timescales to govern the overall efficiency of the process. These steps are divided as follow: (1) photon absorption and excitation (in femtoseconds), (2) charge separation (femto- to picoseconds), (3) charge carrier diffusion/transport (nano- to microseconds), and (4 and 5) reactant activation/conversion and mass transfer (micro- to milliseconds). The identification and quantification of these steps, using the appropriate tool/technique, can provide the guidelines to emphasize the most influential key parameter that improve the overall efficiency and to develop the “photocatalyst by design” concept. In this review, the identification/quantification of reactant activation/conversion and mass transfer (steps 4 and 5) is discussed in details using the in situ/operando techniques, especially the infrared (IR), Raman, and X-ray absorption spectroscopy (XAS). The use of these techniques in photocatalysis was highlighted by the most recent and conclusive case studies which allow a better characterization of the active site and reveal the reaction pathways in order to establish a structure–performance relationship. In each case study, the reaction conditions and the reactor design for photocatalysis (pressure, temperature, concentration, etc.) were thoroughly discussed. In the last part, some examples in the use of time-resolved techniques (time-resolved FTIR, photoluminescence, and transient absorption) are also presented as an author’s guideline to study the elemental steps in photocatalysis at shorter timescale (ps, ns, and µs).

Nanotechnology has emerged as an extraordinary and rapidly developing discipline of science. It has remolded the fate of the whole world by providing diverse horizons in different fields. Nanomaterials are appealing because of their incredibly small size and large surface area. Apart from the naturally occurring nanomaterials, synthetic nanomaterials are being prepared on large scales with different sizes and properties. Such nanomaterials are being utilized as an innovative and green approach in multiple fields. To expand the applications and enhance the properties of the nanomaterials, their functionalization and engineering are being performed on a massive scale. The functionalization helps to add to the existing useful properties of the nanomaterials, hence broadening the scope of their utilization. A large class of covalent and non-covalent functionalized nanomaterials (FNMs) including carbons, metal oxides, quantum dots, and composites of these materials with other organic or inorganic materials are being synthesized and used for environmental remediation applications including wastewater treatment. This review summarizes recent advances in the synthesis, reporting techniques, and applications of FNMs in adsorptive and photocatalytic removal of pollutants from wastewater. Future prospects are also examined, along with suggestions for attaining massive benefits in the areas of FNMs.

(Sun)Light is an abundantly available sustainable source of energy that has been used in catalyzing chemical reactions for several decades now. In particular, studies related to the interaction of light with plasmonic nanostructures have been receiving increased attention. These structures display the unique property of localized surface plasmon resonance, which converts light of a specific wavelength range into hot charge carriers, along with strong local electromagnetic fields, and/or heat, which may all enhance the reaction efficiency in their own way. These unique properties of plasmonic nanoparticles can be conveniently tuned by varying the metal type, size, shape, and dielectric environment, thus prompting a research focus on rationally designed plasmonic hybrid nanostructures. In this review, the term “hybrid” implies nanomaterials that consist of multiple plasmonic or non-plasmonic materials, forming complex configurations in the geometry and/or at the atomic level. We discuss the synthetic techniques and evolution of such hybrid plasmonic nanostructures giving rise to a wide variety of material and geometric configurations. Bimetallic alloys, which result in a new set of opto-physical parameters, are compared with core–shell configurations. For the latter, the use of metal, semiconductor, and polymer shells is reviewed. Also, more complex structures such as Janus and antenna reactor composites are discussed. This review further summarizes the studies exploiting plasmonic hybrids to elucidate the plasmonic-photocatalytic mechanism. Finally, we review the implementation of these plasmonic hybrids in different photocatalytic application domains such as H₂ generation, CO₂ reduction, water purification, air purification, and disinfection.

The Diels–Alder reaction (DAR) is found in myriad applications in organic synthesis and medicinal chemistry for drug development, as it is the method of choice for the expedient synthesis of complex natural compounds and innovative materials including nanomaterials, graphene expanses, and polymeric nanofibers. Furthermore, the greatest focus of attention of DARs is on the consistent reaction procedure with stimulus yields by highly stereo- and regioselective mechanistic pathways. Therefore, the present review is intended to summarize conventional solvent-free (SF) DARs for the expedient synthesis of heterocyclic compounds and materials. In particular, this review deals with the DARs of mechanochemical grinding, catalysis (including stereoselective catalysts), thermal, and electromagnetic radiation (such as microwave [MW], infrared [IR], and ultraviolet [UV] irradiation) in SF procedures. Therefore, this comprehensive review validates the application of DARs to pharmaceutical innovations and biorenewable materials through consistent synthetic approaches.

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Zirconium is a silvery-white malleable and ductile metal at room temperature with a crustal abundance of 162 ppm. Its compounds, showing Lewis acidic behavior and high catalytic performance, have been recognized as a relatively cheap, low-toxicity, stable, green, and efficient catalysts for various important organic transformations. Commercially available inorganic zirconium chloride was widely applied as a catalyst to accelerate amination, Michael addition, and oxidation reactions. Well-designed zirconocene perfluorosulfonates can be applied in allylation, acylation, esterification, etc. N-Chelating oganozirconium complexes accelerate polymerization, hydroaminoalkylation, and CO₂ fixation efficiently. In this review, the applications of both commercially available and synthesized zirconium catalysts in organic reactions in the last 5 years are highlighted. Firstly, the properties and application of zirconium and its compounds are simply introduced. After presenting the superiority of zirconium compounds, their applications as catalysts to accelerate organic transformations are classified and presented in detail. On the basis of different kinds of zirconium catalysts, organic reactions accelerated by inorganic zirconium catalysts, zirconium catalysts bearing Cp, and organozirconium catalysts without Cp are summarized, and the plausible reaction mechanisms are presented if available.

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This review article emphasizes the C–C bond cleavage in organic synthesis via metal-free approach. Conventional organic synthesis mainly deals with the reactive π bonds and polar σ bonds. In contrast, the ubiquitous C–C single bonds are inherently stable and are less reactive, which poses a challenge to synthetic chemists. Although inert, such C–C single-bond cleavage reactions have gained attention amongst synthetic chemists, as they provide unique and more straightforward routes, with significantly fewer steps. Several review articles have been reported regarding the activation and cleavage of C–C bonds using different transition metals. However, given the high cost and toxicity of many of these metals, the development of strategies under metal-free conditions is of utmost importance. Though many research articles have been published in this area, no review article has been reported so far. Herein, we discuss the reactions in a more concise way from the year 2012 to today, with emphasis on important reactions. Mechanisms of all the reactions are also well addressed. We believe that this review will be beneficial for the readers who work in this field.

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Directed transformation of available natural compounds with native biological activity is a promising area of research in organic and medicinal chemistry aimed at finding effective drug substances. The number of scientific publications devoted to the transformation of natural compounds and investigations of their pharmacological properties, in particular, monoterpenes and their nearest derivatives, increases every year. At the same time, the chemistry of nitrogen-containing heterocyclic compounds has been actively developed since the 1950s after the news that the benzimidazole core is an integral part of the structure of vitamin B₁₂. At the time of writing this review, the data on chemical modifications of monoterpenes and their nearest derivatives leading to formation of compounds with a nitrogen-containing heterocycle core have not been summarized and systematized in terms of chemical transformations. In this review, we tried to summarize the literature data on the preparation and properties of nitrogen-containing heterocyclic compounds synthesized from monoterpenes/monoterpenoids and their nearest derivatives for the period from 2000 to 2021.