Topics in Current Chemistry最新文献

Organophosphorus compounds have long been considered valuable in both organic synthesis and life science. P(III)-nucleophiles, such as phosphites, phosphonites, and diaryl/alkyl phosphines, are particularly noteworthy as phosphorylation reagents for their ability to form new P−C bonds, producing more stable, ecofriendly, and cost-effective organophosphorus compounds. These nucleophiles follow similar phosphorylation routes as in the functionalization of P−H bonds and P−OH bonds. Activation can occur through photocatalytic, electrocatalytic, or thermo-driven reactions, often in coordination with a Michaelis–Arbuzov-trpe rearrangement process, to produce the desired products. As such, this review offers a thorough overview of the phosphorylated transformation and potential mechanisms of P(III)-nucleophiles, specifically focusing on developments since 2010. Notably, this review may provide researchers with valuable insights into designing and synthesizing functionalized organophosphorus compounds from P(III)-nucleophiles, guiding future advancements in both research and practical applications.

Graphical Abstract

Halide perovskite nanocrystals (HPNCs) are currently among the most intensely investigated group of materials. Structurally related to the bulk halide perovskites (HPs), HPNCs are nanostructures with distinct chemical, optical, and electronic properties and significant practical potential. One of the keys to the effective exploitation of the HPNCs in advanced technologies is the development of controllable, reproducible, and scalable methods for preparation of materials with desired compositions, phases, and shapes and low defect content. Another important condition is a quantitative understanding of factors affecting the chemical stability and the optical and electronic properties of HPNCs. Here we review important recent developments in these areas. Following a brief historical prospective, we provide an overview of known chemical methods for preparation of HPNCs and approaches used to control their composition, phase, size, and shape. We then review studies of the relationship between the chemical composition and optical properties of HPNCs, degradation mechanisms, and effects of charge injection. Finally, we provide a short summary and an outlook. The aim of this review is not to provide a comprehensive summary of all relevant literature but rather a selection of highlights, which, in the subjective view of the authors, provide the most significant recent observations and relevant analyses.

From a synthetic perspective, bis(indolyl)methanes have undergone extensive investigation over the past two to three decades owing to their remarkable pharmacological activities, encompassing anticancer, antimicrobial, antioxidant, and antiinflammatory properties. These highly desirable attributes have spurred significant interest within the scientific community, leading to the development of various synthetic strategies that are not only more efficient but also ecofriendly. This synthesis-based literature review delves into the advancements made in the past 5 years, focusing on the synthesis of symmetrical as well as unsymmetrical bis(indolyl)methanes. The review encompasses a wide array of methods, ranging from well-established techniques to more unconventional and innovative approaches. Furthermore, it highlights the exploration of various substrates, encompassing readily available chemicals such as indole, aldehydes/ketones, indolyl methanols, etc. as well as the use of some specific compounds as starting materials to achieve the synthesis of this invaluable molecule. By encapsulating the latest developments in this field, this review provides insights into the expanding horizons of bis(indolyl)methane synthesis.

The kinetically inert, six coordinated, octahedral Pt(IV) complexes are termed dual-, triple-, or multi-action prodrugs based on the nature of the axially substituted ligands. These ligands are either inert or biologically active, where the nature of these axial ligands provides additional stability, synergistic biological activity or cell-targeting ability. There are many literature reports from each of these classes, mentioning the varied nature of these axial ligands. The ligands comprise drug molecules such as chlorambucil, doxorubicin, valproic acid, ethacrynic acid, biologically active chalcone, coumarin, combretastatin, non-steroidal anti-inflammatory drugs (NSAIDs) and many more, potentiating the anti-proliferative profile or reducing the side effects associated with cisplatin therapy. The targeting and non-targeting nature of these moieties exert additive or synergistic effects on the anti-cancer activity of Pt(II) moieties. Herein, we discuss the effects of these axially oriented ligands and the changes in the non-leaving am(m)ine groups and in the leaving groups on the biological activity. In this review, we have presented the latest developments in the field of Pt(IV) complexes that display promising activity with a reduced resistance profile. We have discussed the structure activity relationship (SAR) and the effects of the ligands on the biological activity of Pt(IV) complexes with cisplatin, oxaliplatin, carboplatin and the Pt core other than approved drugs. This literature work will help researchers to get an idea about Pt(IV) complexes that have been classified based on the aspects of their biological activity.

Visualization of biomolecules in their native environment or imaging-aided understanding of more complex biomolecular processes are one of the focus areas of chemical biology research, which requires selective, often site-specific labeling of targets. This challenging task is effectively addressed by bioorthogonal chemistry tools in combination with advanced synthetic biology methods. Today, the smart combination of the elements of the bioorthogonal toolbox allows selective installation of multiple markers to selected targets, enabling multicolor or multimodal imaging of biomolecules. Furthermore, recent developments in bioorthogonally applicable probe design that meet the growing demands of superresolution microscopy enable more complex questions to be addressed. These novel, advanced probes enable highly sensitive, low-background, single- or multiphoton imaging of biological species and events in live organisms at resolutions comparable to the size of the biomolecule of interest. Herein, the latest developments in bioorthogonal fluorescent probe design and labeling schemes will be discussed in the context of in cellulo/in vivo (multicolor and/or superresolved) imaging schemes. The second part focuses on the importance of genetically engineered minimal bioorthogonal tags, with a particular interest in site-specific protein tagging applications to answer biological questions.

Third-generation organic light-emitting diodes (OLEDs) based on metal-free thermally activated delayed fluorescent (TADF) materials have sparked tremendous interest in the last decade due to their nearly 100% exciton utilization efficiency, which can address the low-efficiency issue of the first-generation fluorescent emitters and the high-cost issue of the second-generation organometallic phosphorescent emitters. Construction of efficient and stable TADF-OLEDs requires utilizing TADF materials with a narrow singlet–triplet energy gap (ΔE_ST), high photoluminescence quantum yield (PLQY) and short TADF lifetime. A small ΔE_ST is necessary for an efficient reverse intersystem crossing (RISC) process, which can be achieved through the effective spatial separation of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). TADF emitters have been generally designed as intramolecular charge transfer (ICT) molecules with highly twisted donor–acceptor (D–A) molecular architectures. A wide variety of combinations of electron donors and acceptors have been explored. In this review, we shall focus on recent progress in organic TADF molecules incorporating strong electron-donor phenoxazine moiety and their application as emitting layer (EML) in OLEDs.

Graphical Abstract

Pyrimidine is a pharmacologically important moiety that exhibits diverse biological activities. This review reflects the growing significance of transition metal-catalyzed reactions for the synthesis of pyrimidines (with no discussion being made on the transition metal-catalyzed functionalization of pyrimidines). The effect of different catalysts on the selectivity/yields of pyrimidines and catalyst recyclability (wherever applicable) are described, together with attempts to illustrate the role of the catalyst through mechanisms. Although several methods have been researched for synthesizing this privileged scaffold, there has been a considerable push to expand transition metal-catalyzed, sustainable, efficient and selective synthetic strategies leading to pyrimidines. The aim of the authors with this update (2017–2023) is to drive the designing of new transition metal-mediated protocols for pyrimidine synthesis.

Graphical Abstract

Amination reactions play a pivotal role in synthetic organic chemistry, facilitating the generation of nitrogen-containing scaffolds with broad applications in drug synthesis, material production, polymer formation, and the generation of amino acids and peptides. Amination offers the potential to fine tune the properties of natural products and produce functional materials for various applications. Palladium N-heterocyclic carbene (Pd–NHC) emerges as an innovative and highly effective catalyst in this context. Under favorable reaction conditions, this robust and simple catalyst efficiently facilitates the synthesis of a diverse range of compounds with varying complexity and utility. Pd–NHC complexes exhibit significant σ-electron donating potential, enhancing the ease of the oxidative addition process in their mechanistic pathway. Their steric topography further contributes to a rapid reductive elimination. These complexes demonstrate remarkable stability, a result of the strong Pd–ligand bond. The wide variety of Pd–NHC complexes has proven highly efficient in catalyzing reactions across a spectrum of complexities, from simple to intricate. The domain of aminations catalyzed by Pd–NHC has undergone significant diversification, presenting new opportunities, particularly in the realms of material chemistry and natural product synthesis. This review outlines the advancements in Pd–NHC-catalyzed amination reactions, covering literature up to date.

Graphical Abstract

Palladium (Pd) N-heterocyclic carbenes (NHCs) have amassed high recognition recently. They are efficient complexes with tuneable complexities promoting catalysis significantly. Amination reactions have paved way toward the formation of C–N bonds and, in turn, realizing structurally relevant molecules in organic chemistry. Inspired by these facets, we have tried to encompass in this review, the developments in Pd–NHC-catalyzed amination reactions and carries reports up to date.

While bioorthogonal reactions are routinely employed in living cells and organisms, their application within individual organelles remains limited. In this review, we highlight diverse examples of bioorthogonal reactions used to investigate the roles of biomolecules and biological processes as well as advanced imaging techniques within cellular organelles. These innovations hold great promise for therapeutic interventions in personalized medicine and precision therapies. We also address existing challenges related to the selectivity and trafficking of subcellular dynamics. Organelle-targeted bioorthogonal reactions have the potential to significantly advance our understanding of cellular organization and function, provide new pathways for basic research and clinical applications, and shape the direction of cell biology and medical research.

Light-induced bioorthogonal reactions offer spatiotemporal control over selective biomolecular labeling. This review covers the recent advances in the design of photo-activatable reagents for bioorthogonal conjugation reactions in living systems. These reagents are stable in the absence of light, but transformed into reactive species upon light illumination, which then undergo rapid ligation reactions. The light wavelength has been tuned from ultraviolet to near infrared to enable efficient photo-activation in reactions in deep tissues. The most prominent photo-activatable reagents are presented, including tetrazoles, tetrazines, 9,10-phenanthrenequinone, diarylsydnones, and others. A particular focus is on the strategies for improving reaction kinetics and biocompatibility accomplished through careful molecular engineering. The utilities of these photo-activatable reagents are illustrated through a broad range of biological applications, including in vivo protein labeling, positron emission tomography (PET) imaging, responsive hydrogels, and fluorescence microscopy. The further development and optimization of these biocompatible photo-activatable reagents should lead to new chemical biology strategies for studying biomolecular structure and function in living systems.