Rammohan A, Krinochkin AP, Khasanov AF
… +2 more, Kopchuk DS, Zyryanov GV
Top Curr Chem (Cham)
· 2022 Aug · PMID 35951264
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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...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.
Chernyshov VV, Popadyuk II, Yarovaya OI
… +1 more, Salakhutdinov NF
Top Curr Chem (Cham)
· 2022 Aug · PMID 35951263
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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 scientif...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 B. 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.
Top Curr Chem (Cham)
· 2022 Aug · PMID 35951165
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(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 na...(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 H generation, CO reduction, water purification, air purification, and disinfection.
Peng L, Zhao Y, Yang T
… +4 more, Tong Z, Tang Z, Orita A, Qiu R
Top Curr Chem (Cham)
· 2022 Aug · PMID 35951161
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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 rel...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 CO 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.
Zhang S, Malik S, Ali N
… +3 more, Khan A, Bilal M, Rasool K
Top Curr Chem (Cham)
· 2022 Aug · PMID 35951126
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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 beca...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.
Issa Hamoud H, Wolski L, Pankin I
… +3 more, Bañares MA, Daturi M, El-Roz M
Top Curr Chem (Cham)
· 2022 Aug · PMID 35951125
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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 femto...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).
Top Curr Chem (Cham)
· 2022 Aug · PMID 35948820
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Cyclometalated Ir(III) complexes exhibit strong phosphorescence emission with lifetime of submicroseconds to several microseconds at room temperature. Their synthetic versatility enables broad control of physical propert...Cyclometalated Ir(III) complexes exhibit strong phosphorescence emission with lifetime of submicroseconds to several microseconds at room temperature. Their synthetic versatility enables broad control of physical properties, such as charge and lipophilicity, as well as emission colors. These favorable properties have motivated the use of Ir(III) complexes in luminescent bioimaging applications. This review examines the recent progress in the development of phosphorescent biolabels and sensors based on Ir(III) complexes. It begins with a brief introduction about the basic principles of the syntheses and photophysical processes of cyclometalated Ir(III) complexes. Focus is placed on illustrating the broad imaging utility of Ir(III) complexes. Phosphorescent labels illuminating intracellular organelles, including mitochondria, lysosomes, and cell membranes, are summarized. Ir(III) complexes capable of visualization of tumor spheroids and parasites are also introduced. Facile chemical modification of the cyclometalating ligands endows the Ir(III) complexes with strong sensing ability. Sensors of temperature, pH, CO, metal ions, anions, biosulfur species, reactive oxygen species, peptides, and viscosity have recently been added to the molecular imaging tools. This diverse utility demonstrates the potential of phosphorescent Ir(III) complexes toward bioimaging applications.
Aoki S, Yokoi K, Hisamatsu Y
… +3 more, Balachandran C, Tamura Y, Tanaka T
Top Curr Chem (Cham)
· 2022 Aug · PMID 35948812
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Cyclometalated iridium(III) (Ir(III)) complexes exhibit excellent photophysical properties that include large Stokes shift, high emission quantum yields, and microsecond-order emission lifetimes, due to low-lying metal-t...Cyclometalated iridium(III) (Ir(III)) complexes exhibit excellent photophysical properties that include large Stokes shift, high emission quantum yields, and microsecond-order emission lifetimes, due to low-lying metal-to-ligand charge transfer (spin-forbidden singlet-triplet (MLCT) transition). As a result, analogs have been applied for research not only in the material sciences, such as the development of organic light-emitting diodes (OLEDs), but also for photocatalysts, bioimaging probes, and anticancer reagents. Although a variety of methods for the synthesis and the applications of functionalized cyclometalated iridium complexes have been reported, functional groups are generally introduced to the ligands prior to the complexation with Ir salts. Therefore, it is difficult to introduce thermally unstable functional groups such as peptides and sugars due to the harsh reaction conditions such as the high temperatures used in the complexation with Ir salts. In this review, the functionalization of Ir complexes after the formation of cyclometalated Ir complexes and their biological and material applications are described. These methods are referred to as "post-complexation functionalization (PCF)." In this review, applications of PCF to the design and synthesis of Ir(III) complexes that exhibit blue -red and white color emissions, luminescence pH probes, luminescent probes of cancer cells, compounds that induce cell death in cancer cells, and luminescent complexes that have long emission lifetimes are summarized.
Top Curr Chem (Cham)
· 2022 Jun · PMID 35737142
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The molecules possessing triazine and tetrazine moieties belong to a special class of heterocyclic compounds. Both triazines and tetrazines are building blocks and have provided a new dimension to the design of biologica...The molecules possessing triazine and tetrazine moieties belong to a special class of heterocyclic compounds. Both triazines and tetrazines are building blocks and have provided a new dimension to the design of biologically important organic molecules. Several of their derivatives with fine-tuned electronic properties have been identified as multifunctional, adaptable, switchable, remarkably antifungal, anticancer, antiviral, antitumor, cardiotonic, anti-HIV, analgesic, anti-protozoal, etc. The objective of this review is to comprehensively describe the recent developments in synthesis, coordination properties, and various applications of triazine and tetrazine molecules. The rich literature demonstrates various synthetic routes for a variety of triazines and tetrazines through microwave-assisted, solid-phase, metal-based, [4+2] cycloaddition, and multicomponent one-pot reactions. Synthetic approaches contain linear, angular, and fused triazine and tetrazine heterocycles through a combinatorial method. Notably, the triazines and tetrazines undergo a variety of organic transformations, including electrophilic addition, coupling, nucleophilic displacement, and intramolecular cyclization. The mechanistic aspects of these heterocycles are discussed in a detailed way. The bioorthogonal application of these polyazines with various strained alkenes and alkynes provides a new prospect for investigations in chemical biology. This review systematically encapsulates the recent developments and challenges in the synthesis and possible potential applications of various triazine and tetrazine systems.
Top Curr Chem (Cham)
· 2022 Jun · PMID 35717546
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Conjugated polymers (CPs) have been recently widely investigated for their properties and their applications in different fields including photocatalysis. Among the family of CPs, polypyrrole (PPy) has been the most exte...Conjugated polymers (CPs) have been recently widely investigated for their properties and their applications in different fields including photocatalysis. Among the family of CPs, polypyrrole (PPy) has been the most extensively studied owing to its good environmental stability, high electrical conductivity, superior redox properties and easy synthesis. Besides, nanostructured polypyrrole-based nanomaterials are a type of active organic materials for photocatalysis, which is one of their emerging applications. Nanostructuration of polypyrrole can reduce the electron-hole recombination because of short charge transfer distances and reactant adsorption, and product desorption can be enhanced owing to the high surface area offered by nanostructures. This review summarizes synthesis of different nanostructures based on π-conjugated polymer polypyrrole and the latest developments for photocatalytic applications, including degradation of organic pollutants and hydrogen generation.
Skillen N, Daly H, Lan L
… +6 more, Aljohani M, Murnaghan CWJ, Fan X, Hardacre C, Sheldrake GN, Robertson PKJ
Top Curr Chem (Cham)
· 2022 Jun · PMID 35717466
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Photocatalytic reforming of biomass has emerged as an area of significant interest within the last decade. The number of papers published in the literature has been steadily increasing with keywords such as 'hydrogen' an...Photocatalytic reforming of biomass has emerged as an area of significant interest within the last decade. The number of papers published in the literature has been steadily increasing with keywords such as 'hydrogen' and 'visible' becoming prominent research topics. There are likely two primary drivers behind this, the first of which is that biomass represents a more sustainable photocatalytic feedstock for reforming to value-added products and energy. The second is the transition towards achieving net zero emission targets, which has increased focus on the development of technologies that could play a role in future energy systems. Therefore, this review provides a perspective on not only the current state of the research but also a future outlook on the potential roadmap for photocatalytic reforming of biomass. Producing energy via photocatalytic biomass reforming is very desirable due to the ambient operating conditions and potential to utilise renewable energy (e.g., solar) with a wide variety of biomass resources. As both interest and development within this field continues to grow, however, there are challenges being identified that are paramount to further advancement. In reviewing both the literature and trajectory of the field, research priorities can be identified and utilised to facilitate fundamental research alongside whole systems evaluation. Moreover, this would underpin the enhancement of photocatalytic technology with a view towards improving the technology readiness level and promoting engagement between academia and industry.
Top Curr Chem (Cham)
· 2022 Jun · PMID 35715540
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Near-infrared (NIR, 700-1700 nm) luminescent imaging is an emerging bioimaging technology with low photon scattering, minimal autofluorescence, deep tissue penetration, and high spatiotemporal resolution that has shown f...Near-infrared (NIR, 700-1700 nm) luminescent imaging is an emerging bioimaging technology with low photon scattering, minimal autofluorescence, deep tissue penetration, and high spatiotemporal resolution that has shown fascinating promise for NIR imaging-guided theranostics. In recent progress, NIR luminescent metal complexes have attracted substantially increased research attention owing to their intrinsic merits, including small size, anti-photobleaching, long lifetime, and metal-centered NIR emission. In the past decade, scientists have contributed to the advancement of NIR metal complexes involving efforts to improve photophysical properties, biocompatibility, specificity, pharmacokinetics, in vivo visualization, and attempts to exploit new ligand platforms. Herein, we summarize recent progress and provide future perspectives for NIR metal complexes, including d-block transition metals and f-block lanthanides (Ln) as NIR optical molecular probes for bioassays.
Top Curr Chem (Cham)
· 2022 Jun · PMID 35701677
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Metal complex luminophores have seen dramatic expansion in application as imaging probes over the past decade. This has been enabled by growing understanding of methods to promote their cell permeation and intracellular...Metal complex luminophores have seen dramatic expansion in application as imaging probes over the past decade. This has been enabled by growing understanding of methods to promote their cell permeation and intracellular targeting. Amongst the successful approaches that have been applied in this regard is peptide-facilitated delivery. Cell-permeating or signal peptides can be readily conjugated to metal complex luminophores and have shown excellent response in carrying such cargo through the cell membrane. In this article, we describe the rationale behind applying metal complexes as probes and sensors in cell imaging and outline the advantages to be gained by applying peptides as the carrier for complex luminophores. We describe some of the progress that has been made in applying peptides in metal complex peptide-driven conjugates as a strategy for cell permeation and targeting of transition metal luminophores. Finally, we provide key examples of their application and outline areas for future progress.
Wu M, Zhang Z, Yong J
… +4 more, Schenk PM, Tian D, Xu ZP, Zhang R
Top Curr Chem (Cham)
· 2022 Jun · PMID 35695976
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Luminescence chemosensors are one of the most useful tools for the determination and imaging of small biomolecules and ions in situ in real time. Based on the unique photo-physical/-chemical properties of ruthenium(II) (...Luminescence chemosensors are one of the most useful tools for the determination and imaging of small biomolecules and ions in situ in real time. Based on the unique photo-physical/-chemical properties of ruthenium(II) (Ru(II)) complexes, the development of Ru(II) complex-based chemosensors has attracted increasing attention in recent years, and thus many Ru(II) complexes have been designed and synthesized for the detection of ions and small biomolecules in biological and environmental samples. In this work, we summarize the research advances in the development of Ru(II) complex-based chemosensors for the determination of ions and small biomolecules, including anions, metal ions, reactive biomolecules and amino acids, with a particular focus on binding/reaction-based chemosensors for the investigation of intracellular analytes' evolution through luminescence analysis and imaging. The advances, challenges and future research directions in the development of Ru(II) complex-based chemosensors are also discussed.
Top Curr Chem (Cham)
· 2022 Jun · PMID 35662375
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With the ever-increasing demand for energy in the world, the tendency to use renewable energies has been growing rapidly. Sunlight, as an inexhaustible energy source, and the oceans, as one of the most valuable treasures...With the ever-increasing demand for energy in the world, the tendency to use renewable energies has been growing rapidly. Sunlight, as an inexhaustible energy source, and the oceans, as one of the most valuable treasures on Earth, are available for free. Simultaneous exploitation of these two sources of energy and matter (sunlight and oceans) in one configuration can provide a sustainable solution for future energy supply. Among the various types of such energy storage and conversion systems, solar rechargeable seawater batteries (SRSBs) can meet this need by storing the chemical energy of seawater by receiving solar energy. SRSBs consist of two compartments: a closed compartment including a sodium metal anode in an organic liquid electrolyte, and an open compartment containing a semiconductor photoelectrode immersed in seawater, which are separated from each other by a ceramic solid electrolyte membrane. In this complex system, the photoelectrode is irradiated by sunlight, whereby electrons are excited and reach the Na metal anode after passing though the external circuit. The ceramic solid electrolyte harvests only sodium ions from seawater and transfers them to the anodic part, where the transferred ions are reduced to sodium metal atoms. At the same time, an oxygen evolution reaction takes place at the cathodic part. In this way, the battery is charged. The use of a photoelectrode in the charging process significantly increases the voltage efficiency of SRSBs to more than 90%, whereas a cell with only the seawater compartment (without a photoelectrode) will not deliver satisfactory performance. Therefore, to achieve very high efficiencies, designing an accurate system with the best components is absolutely necessary. This review focuses on the working principle of SRSBs, at the same time explaining the effect of key components on the performance and stability of SRSBs. The role of the semiconductor photoelectrode in improving the voltage efficiency of SRSBs is also described in detail, and finally strategies proposed to overcome obstacles to the commercialization of SRSBs are introduced.
Jiang Z, Mahmood EA, Harofteh NZ
… +3 more, Ebadi AG, Toughani M, Vessally E
Top Curr Chem (Cham)
· 2022 May · PMID 35606628
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Direct reductive N-methylation of inexpensive and readily available nitro compounds as raw material feedstocks is more attractive and straightforward compared with conventional N-methylation of amines to prepare biologic...Direct reductive N-methylation of inexpensive and readily available nitro compounds as raw material feedstocks is more attractive and straightforward compared with conventional N-methylation of amines to prepare biologically and pharmaceutically important N-methylated amine derivatives. This strategy for synthesis of N-methylamines avoids prepreparation of NH-free amines and therefore significantly shortens the separation and purification steps. In recent years, numerous methylating agents and catalytic systems have been reported for this appealing transformation. Thus, it is an appropriate time to summarize such advances. This review elaborates on the most important discoveries and advances in this research arena, with special emphasis on the mechanistic aspect of reactions that may provide new insights into catalyst improvement.
Haese M, Winterhalter K, Jung J
… +1 more, Schmidt MS
Top Curr Chem (Cham)
· 2022 May · PMID 35595946
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Fischer glycosylation is typically the chemical reaction of a monosaccharide and an alcohol in presence of an acidic catalyst to afford glycosides in pyranosidic and furanosidic forms. This reaction is still applied toda...Fischer glycosylation is typically the chemical reaction of a monosaccharide and an alcohol in presence of an acidic catalyst to afford glycosides in pyranosidic and furanosidic forms. This reaction is still applied today for the synthesis of specialized glycosides, and optimization and modification of the method have continued since its discovery by Emil Fischer in the 1890s. This review presents advancements in Fischer glycosylation described in literature of the past 15 years and its implementation in modern chemical methods.
Gao Y, Jiang S, Mao ND
… +6 more, Xiang H, Duan JL, Ye XY, Wang LW, Ye Y, Xie T
Top Curr Chem (Cham)
· 2022 May · PMID 35585362
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Since their discovery in 1970s, Katritzky salts have emerged as one of the most important classes of building blocks for use in organic synthesis and drug discovery. These bulky pyridinium salts derived from alkylamine c...Since their discovery in 1970s, Katritzky salts have emerged as one of the most important classes of building blocks for use in organic synthesis and drug discovery. These bulky pyridinium salts derived from alkylamine can readily generate alkyl radical and undergo a variety of organic transformation reactions such as alkylation, arylation, alkenylation, alkynylation, carbonylation, sulfonylation, and borylation. Through these transformations, complexed molecules bearing new C-C, C-B, or C-S bonds can be constructed in easy ways and in simple steps. This review aims to summarize recent advances in these versatile building blocks in well-classified categories. Representative examples and their reaction mechanisms are discussed. The hope is to provide the scientific community with convenient access to collective information and accelerate further research.
1H-Indole-3-carbaldehyde and related members of the indole family are ideal precursors for the synthesis of active molecules. 1H-Indole-3-carbaldehyde and its derivatives are essential and efficient chemical precursors f...1H-Indole-3-carbaldehyde and related members of the indole family are ideal precursors for the synthesis of active molecules. 1H-Indole-3-carbaldehyde and its derivatives are essential and efficient chemical precursors for generating biologically active structures. Multicomponent reactions (MCRs) offer access to complex molecules. This review highlights the recent applications of 1H-indole-3-carbaldehyde in such inherently sustainable multicomponent reactions from the period, 2014 to 2021 and provides an overview of the field that awaits further exploitation in the assembly of pharmaceutically interesting scaffolds.
Photon upconversion (UC) based on triplet-triplet annihilation (TTA) is considered one of the most attractive methodologies for switching wavelengths from lower to higher energy. This two-photon process, which requires t...Photon upconversion (UC) based on triplet-triplet annihilation (TTA) is considered one of the most attractive methodologies for switching wavelengths from lower to higher energy. This two-photon process, which requires the involvement of a bimolecular system, has been widely used in numerous fields such as bioimaging, solar cells, displays, drug delivery, and so on. In the last years, we have witnessed the harnessing of this concept by the organic community who have developed new strategies for synthetic purposes. Interestingly, the generation of high-energetic species by this phenomenon has provided the opportunity not only to photoredox activate compounds with high-energy demanding bonds, expanding the reactivity window that lies outside the energy window of the initial irradiation wavelength, but also to sensitized conventional photocatalysts through energy transfer processes even employing infrared irradiation. Herein, an overview of the principal examples found in literature is described where TTA-UC systems are found to be suitable photosensitizers for several chemical transformations.