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Phenolic compounds are ubiquitous in nature because of their unique physical and chemical properties and wide applications, which have received extensive research attention. Phenolic compounds represented by tannic acid (TA) play an important role at the nanoscale. TA with a polyphenol hydroxyl structure can chemically react with organic or inorganic materials, among which metal–phenolic networks (MPNs) formed by coordination with metal ions and polyphenol derivatives formed by interactions with organic matter, exhibit specific properties and functions, and play key roles in photo(electro)catalysis. In this paper, we first introduce the fundamental properties of TA, then summarize the factors influencing the properties of MPNs and structural transformation of polyphenol-derived materials. Subsequently, the functions of MPNs and polyphenol derivatives in photo(electro)catalysis reactions are summarized, encompassing improving interfacial charge carrier separation, accelerating surface reaction kinetics, and enhancing light absorption. Finally, this article provides a comprehensive overview of the challenges and outlook associated with MPNs. Additionally, it presents novel insights into their stability, mechanistic analysis, synthesis, and applications in photo(electro)catalysis. [ABSTRACT FROM AUTHOR]

This paper describes iron/photoredox dual-catalyzed acyl nitrene formation and the use of acyl nitrene in constructing various C–O bonds towards phthalides. The developed reaction starts from N-methoxyl-2-alkylbenzamides. Mechanism surveys suggest the reaction involves iron nitrene-based hydrogen atom abstraction (HAA), radical-polar crossover and O-nucleophilic SN1. Distinctively, the often-reported radical rebound in previous publications is not observed. The reaction represents the first example on acyl nitrene-based synthesis of phthalides. Moreover, it also serves as a supplement for the synthesis of marketed medicines such as 3-butylphthalides (NBP), thalidomide, Pomalyst and Otezia. [ABSTRACT FROM AUTHOR]

Using microflow space, a catalytic effect was achieved for supramolecular polymerization. With increasing reactivity at the polymer end, the selective connection of active monomers formed new block domains, avoiding fast homo-assembly. Binding of less-reactive monomers at the polymer end overcame steric bulkiness, affording a stable supramolecular diblock copolymer (SdiBCP). [ABSTRACT FROM AUTHOR]

Ultrathin catalysts predominantly expose surface active atoms to deliver promising applications in oxygen reduction reactions (ORRs). However, they are commonly synthesized at high reaction temperatures, with tedious chemical routes involved. Herein, we report a low temperature (273 K) electric field driven route to synthesize zigzag-surface ultrathin copper nanowires. Interestingly, the ultrathin copper nanowires assemble into three-dimensional microspheres, which exhibit hydrophobic-aerophilic features, eventually resulting in good ORR activities. The aerophilicity and hydrophobicity of copper nanowires are related to their Cu2O active sites and hierarchical protuberances, respectively. Our findings open a new door to grow ultrathin catalysts for new energy storage systems. [ABSTRACT FROM AUTHOR]

A water oxidation catalyst Ru-bcs (bcs = 2,2′-bipyridine-6′-carboxylate-6-sulfonate) with a hybrid ligand was reported. Ru-bcs utilizes the electron-donating properties of carboxylate ligands and the on-demand coordination feature of sulfonate ligands to enable a low onset potential of 1.21 V vs. NHE and a high TOF over 1000 s−1 at pH 7. The adaptive chemistry uncovered in this work provides new perspectives for developing molecular catalysts with high efficiency under low driving forces. [ABSTRACT FROM AUTHOR]

Organosilanes have secured a special place in the synthetic world for several decades. However, among them, allylsilanes are a choice reagent for organic chemists to develop novel organic transformations. In recent years researchers have proved that visible-light photoredox catalysis has emerged as one of the most mild, sustainable, straightforward, and efficient strategies to construct simple to complex molecules with or without enantioselectivity. This review provides an in-depth analysis of recent advances and strategies employed in visible-light photoredox catalysis for allylsilane and its analogues for the development of various organic transformations. The review is divided into sections, each focused on a specific reactivity of allylsilane under light irradiation with C(sp2) center arene or alkene, C(sp2) center carbonyl, and C(sp3) center carbon functionality. In this review, we present optimization data, reaction scope, and mechanistic aspects to bring forward specific reactivity and selectivity trends of allylsilane in photoredox conditions. [ABSTRACT FROM AUTHOR]

A sustainable C(sp2)–C(sp3) cross-electrophile coupling was developed between readily available 5-bromophthalide and 1-benzyl-4-iodopiperidine under micellar conditions, leading to a key intermediate of one of our development compounds. Copper was found to play a crucial role as a co-catalyst in this dual catalysis system. The chemistry and process were successfully demonstrated in a kilo scale to deliver sufficient drug substance to the clinical campaigns. This is the first reported scale-up of such a challenging cross-electrophilic coupling that uses an aqueous medium, and not undesirable reprotoxic polar aprotic solvents (e.g. DMF, DMAc, and NMP). [ABSTRACT FROM AUTHOR]

The search for alternative gold catalyst activators has led us to consider the design of platforms in which a phosphine gold chloride moiety could be activated via formation of a pnictogen bond with a neighboring antimony unit. Here, we describe that such a system can be accessed from 4-(diphenylphosphino)-5-(diphenylstibino)-2,7-di-tert-butyl-9,9-dimethylxanthene, by oxidation of the stibine with 3,5-di-tert-butyl-o-benzoquinone and by coordination of an AuCl unit to the phosphine. This strategy affords a complex in which a Lewis acidic or pnictogen-bond donor catecholatostiborane unit flanks the adjacent gold chloride moiety. This design impacts the catalytic reactivity of the gold center, as reflected by the ability of this complex to catalyze propargyl amide cyclization reactions. Comparisons with a phosphinostiborane ferrocene analog and computations point to the formation of an intramolecular Au–Cl → Sb(V) interaction as responsible for the observed catalytic activity. [ABSTRACT FROM AUTHOR]

A visible light-enabled synthesis of unsymmetrical ketones has been accomplished by the cross-coupling of α,β-unsaturated carboxylic acids and aryldiazonium salts embracing a synergistic eosin Y and Co(OAc)2·4H2O catalysis. The reaction involves decarboxylative aerobic C＝C bond cleavage, and is endowed with the creation of new C–C and C–O bonds with good substrate scope. [ABSTRACT FROM AUTHOR]

Bioorthogonal catalysis, a class of catalytic reactions that are mediated by abiotic metals and proceed in biological environments without interfering with native biochemical reactions, has gained ever-increasing momentum in prodrug delivery over the past few decades. Albeit great progress has been attained in developing new bioorthogonal catalytic reactions and optimizing the catalytic performance of transition metal catalysts (TMCs), the use of TMCs to activate chemotherapeutics at the site of interest in vivo remains a challenging endeavor. To translate the bioorthogonal catalysis-mediated prodrug activation paradigm from flasks to animals, TMCs with targeting capability and stimulus-responsive behavior have been well-designed to perform chemical transformations in a controlled manner within highly complex biochemical systems, rendering on-demand drug activation to mitigate off-target toxicity. Here, we review the recent advances in the development of controllable bioorthogonal catalysis systems, with an emphasis on different strategies for engineering TMCs to achieve precise control over prodrug activation. Furthermore, we outline the envisaged challenges and discuss future directions of controllable bioorthogonal catalysis for disease therapy. [ABSTRACT FROM AUTHOR]

Sonogashira coupling is one of the Nobel reactions discovered in 1975 to form a C–C bond using palladium and copper as co-catalysts. Incorporating alkyne functionalities either in macro or micro molecules by using this Sonogashira reaction has already proven its viability and relevance in the sphere of synthetic chemistry. While aiming for sustainable chemistry, in recent years, visible light photoredox catalysts have appeared as an advanced tool in this regard. In this review, we aim to portray a comprehensive summary of modern visible light photo redox catalyzed Sonogashira reaction, which will leave space for the readers to rethink alternative strategies to conduct the Sonogashira reaction. This review briefly describes the implementation of various metal-based nanomaterial photocatalysts, developing either copper or palladium-free photocatalytic methods, and organo-photolytic and bioinspired photocatalysts for the Sonogashira coupling reactions. Besides, this review also gives a concise overview of the mechanistic aspects and highlights selective examples for substrate scope. [ABSTRACT FROM AUTHOR]

Through the catalysis system design of in situ Ru SACs (single atoms) anchored on a rGO/NC two-dimensional interface, we successfully realized the SA-Ru@rGO/NC electrocatalyst with high metal loading density at a relatively low temperature. The largest NH3 yield of 110.1 μg h−1 mgcat−1 and FE of 17.9% were achieved at −0.3 V under ambient conditions. The electronic environment of the catalyst was regulated by the electronic metal–support interaction, and the use of SACs had the advantages of inhibiting the hydrogen evolution reaction (HER) and enhancing N2 adsorption, which effectively improved the performance of electrocatalytic nitrogen fixation. [ABSTRACT FROM AUTHOR]

This article covers historical and recent efforts to catalyse the dehydrocoupling of amines and silanes, a direct method for Si–N bond formation that offers hydrogen as a byproduct. In some applications, this transformation can be used as a sustainable replacement for traditional aminosilane synthesis, which demands corrosive chlorosilanes while generating one equivalent of ammonium salt waste for each Si–N bond that is formed. These advantages have driven the development of Si–N dehydrocoupling catalysts that span the periodic table, affording mechanistic insight that has led to advances in efficiency and selectivity. Given the divergence in precursors being used, characterization methods being relied on, and applications being targeted, this article highlights the formation of monomeric aminosilanes separately from oligomeric and polymeric aminosilanes. A recent study that allowed for the manganese catalysed synthesis of perhydropolysilazane and commercial chemical vapor deposition precursors is featured, and key opportunities for advancing the field of Si–N dehydrocoupling catalysis are discussed. [ABSTRACT FROM AUTHOR]

Synergistic palladium/copper catalysis for asymmetric allylic alkylation of vinylethylene carbonates with aldimine esters has been developed for the synthesis of α-quaternary (Z)-trisubstituted allylic amino acids under mild conditions. This methodology features broad substrate compatibilities in yields of up to 87% and up to 94% ee. A facile scale-up and straightforward conversion to 1,2,3,5-tetrasubstituted pyrrole and 1,2,5,6-tetrahydropyridine bearing chiral quaternary carbon centers verifies the synthetic utility of this method. [ABSTRACT FROM AUTHOR]

Sub-1 nm nanomaterials (SNMs) have attracted attention for their novel structures and size-related properties. In the past decade, various SNMs were synthesized, such as nanowires, nanorings, nanosheets, nanobelts, nanotubes, and other superstructures. We discussed their synthetic strategies systematically, including the ligand pathway and the cluster-nuclei co-assembly pathway. In addition, SNMs exhibit unique size-related properties. Firstly, SNWs show polymer-analogue properties due to their sub-nanometric size and ultrahigh aspect ratio. We illustrate the polymer-analogue properties on both microscopic and macroscopic scales. The macroscopic assemblies of SNWs can be widely applied for organic liquid storage, energy, and optical applications. Finally, we summarized the applications of SNMs in redox catalysis. Their extraordinary catalytic activity is attributed to their large specific surface area and electronic delocalization at the sub-nanometric scale. We hope this feature article can provide new viewpoints on the design and applications of SNMs. [ABSTRACT FROM AUTHOR]

Hybrid materials of metal–organic frameworks (MOFs) and nanoparticles (NPs) have attracted significant attention because of the wide variety of attractive properties derived from the two components. In the last decade, the development of synthesis techniques for NP/MOF composites was particularly significant. In the field of catalysis in particular, various synergistic effects that make the composites attractive catalysts have been reported. However, the role of MOFs in the composite catalysts is still not well understood and is being elucidated. In this feature article, we focus on recent progress in NP/MOF composite catalysts, concentrating on the analysis of the interaction between NPs and MOFs and the reaction mechanisms, together with the synthetic techniques used for NP/MOF hybrid materials. [ABSTRACT FROM AUTHOR]

Covalent immobilization of TEMPO at carbon and gold via an aliphatic –(CH2)6– linker was achieved via cathodic grafting of a diamagnetic precursor, tetramethylpiperidine, with subsequent >NH to >NO oxidation to give TEMPO-capped paramagnetic interfaces (ΓTEMPO = 5.2 × 10−10 mol cm−2); catalytic and spin switching potential of the thus prepared systems was demonstrated. [ABSTRACT FROM AUTHOR]

The site selective C(sp2)–H bond functionalization of olefins has been achieved through a visible-light-induced photoredox-quinuclidine dual catalysis upon merging the quinuclidinium radical cation addition to alkene strategy and the distal heteroaryl ipso-migration strategy. This synthetic protocol features a simple operation with readily available starting materials in good step-economy to access alkenylheteroaromatic products in moderate to good yields under mild conditions. A plausible cascade catalytic reaction mechanism is also proposed. [ABSTRACT FROM AUTHOR]

A summary of the catalytic synthesis and reactivity of N-silylated amines is presented. Dehydrocoupling of amines with silanes, hydrosilylation of imines and dealkenylative coupling of amines with vinylsilanes are three ways to achieve their catalytic syntheses. The resultant N-silylamines serve as substrates in a variety of reactions, including C–N and C–C bond forming reactions, and are preferred in transformations because of the facile Si–N hydrolytic cleavage to reveal free amine products upon reaction completion. This review highlights the distinct electronic properties of N-silyl amines, N-silyl imines and N-silyl enamines that result in complementary reactivity to that of parent non-silyl variants. [ABSTRACT FROM AUTHOR]

The localized surface plasmon resonance (LSPR) of noble metals has been investigated for decades for applications in various catalysis reactions and optical research studies, but its development has been hampered by inefficient light absorption and high costs. In comparison, the creation of less expensive semiconductors (metal oxides) with strong plasmonic absorption is an appealing option, particularly defective molybdenum oxide (HxMoO3−y) has received considerable attention and investigation as a promising plasmonic material for a variety of catalytic reactions (photocatalysis, thermocatalysis, photothermal catalysis, etc.).The LSPR effect of HxMoO3−y can be tuned throughout a broad spectrum range from visible to near-infrared (NIR) by altering the doping amount by electrochemical control, chemical reduction, or photochemical control. Notably, defects (oxygen vacancies) in HxMoO3−y arise in conjunction with the LSPR effect, resulting in the formation of unique and useful active sites in a range of catalytic processes. In this review, we explore the formation mechanism of HxMoO3−y with plasmonic features and discuss its applications in photocatalysis, thermocatalysis, and photothermal catalysis. [ABSTRACT FROM AUTHOR]

Three 3-component copper(I)-based slider-on-deck systems served as catalysts for a click reaction showing a higher catalytic activity with increasing sliding speed. Upon addition of brake stones, the motion of the resulting 4-component machinery was slowed and eventually stopped (on the NMR time scale) with the effect that catalysis was reduced or obstructed. [ABSTRACT FROM AUTHOR]

Radical carbonylation offers potent methods for introducing carbon monoxide into organic molecules. This feature article focuses on our current efforts to develop new strategies for radical carbonylation, which include electron-transfer carbonylation, site-selective C(sp3)–H carbonylation by a photocatalyst and ring-opening carbonylation. [ABSTRACT FROM AUTHOR]

Research on organic cages has blossomed over the past few years into a mature field of study which can contribute to solving some of the challenging problems. In this review we aim to showcase the recent trends in synthesis of organic cages including a brief discussion on their use in catalysis, gas sorption, host–guest chemistry and energy transfer. Among the organic cages, water-soluble analogues are a special class of compounds which have gained renewed attention in recent times. Due to their advantage of being compatible with water, such cages have the potential of showing biomimetic activities and can find use in drug delivery and also as hosts for catalysis in aqueous medium. Hence, the synthetic strategies for the formation of water-soluble organic cages shall be discussed along with their potential applications. [ABSTRACT FROM AUTHOR]

A chiral N,N′-dioxide/cobalt(II) complex catalytic system is developed to promote the multistep cascade reaction of α,β-unsaturated-N-aryl nitrones with allenes, giving a variety of chiral dihydropyridoindoles in moderate to good yields with excellent dr and ee values. Mechanistic studies support a [3+2] cycloaddition/[3,3]-rearrangement/retro-Mannich process. [ABSTRACT FROM AUTHOR]

The introduction of organic functionalities into porous inorganic materials not only makes the resulting hybrid porous framework to be more flexible and hydrophobic, but also provides additional scope for anchoring metal binding sites, which is beneficial for different frontline applications. Furthermore, the nanoscale porosity and high surface area of these organic–inorganic hybrid materials offer a better dispersion of active sites, which greatly enhances their application potential in adsorption, sensing, drug-delivery, energy storage, optoelectronics, light harvesting and catalysis. Easy post-synthetic functionalization of these hybrid materials has widened their application potential. Herein, we highlight several important synthetic strategies to design a wide range of organic–inorganic hybrid porous materials starting from the respective molecular precursors and their task-specific applications in energy and environmental research. We also outline the recent developments in their respective application areas together with various challenges that need to be overcome. [ABSTRACT FROM AUTHOR]

An efficient Pd/Cu bimetallic cross-coupling catalysis of fluoroaryl halides and fluoroarenes is reported. In situ generation of the Cu nucleophile by rate determining C–H activation of highly fluorinated aryls (≥4 F atoms) leads to high cross-coupling selectivity with little formation of homocoupling products. [ABSTRACT FROM AUTHOR]

Treatment of a crown-ether receptor and a silver(I)-loaded cyclam derivative (＝NetState-I) with a fuel acid reversibly afforded the protonated cyclam and the silver(I)-loaded crown ether (＝NetState-II). While NetState-I was catalytically OFF, a base-catalysed Michael addition and a silver(I)-catalysed oxime cyclisation reaction was pulsed under dissipative conditions in NetState-II. [ABSTRACT FROM AUTHOR]

In the last decade, photoredox catalysis has unlocked unprecedented reactivities in synthetic organic chemistry. Seminal advancements in the field have involved the use of well-studied metal complexes as photoredox catalysts (PCs). More recently, the synthetic community, looking for more sustainable approaches, has been moving towards the use of purely organic molecules. Organic PCs are generally cheaper and less toxic, while allowing their rational modification to an increased generality. Furthermore, organic PCs have allowed reactivities that are inaccessible by using common metal complexes. Likewise, in synthetic catalysis, the field of photocatalysis is now experiencing a green evolution moving from metal catalysis to organocatalysis. In this feature article, we discuss and critically comment on the scientific reasons for this ongoing evolution in the field of photoredox catalysis, showing how and when organic PCs can efficiently replace their metal counterparts. [ABSTRACT FROM AUTHOR]

In the context of bioinspired OAT catalysis, we developed a tetradentate dipyrrinpyridine ligand, a hybrid of hemic and non-hemic models. The catalytic activity of the iron(III) derivative was investigated in the presence of iodosylbenzene. Unexpectedly, MS, EPR, Mössbauer, UV-visible and FTIR spectroscopic signatures supported by DFT calculations provide convincing evidence for the involvement of a relevant FeIII–O–NPy active intermediate. [ABSTRACT FROM AUTHOR]

The development of visible-light-induced photoacid catalyzed glycosylation is reported. The eosin Y and PhSSPh catalyst system is applied to realize glycosylation with different glycosyl donors upon light irradiation. The reaction shows a broad substrate scope, including both glycosyl donors and acceptors, and highlights the mild nature of the reaction conditions. [ABSTRACT FROM AUTHOR]

The Tethered Counterion-Directed Catalysis (TCDC) approach has been applied to the enantioselective Au(I) catalyzed dearomatizations of 1-naphthols with allenamides. Stereocontrol is ensured by the intramolecular ion-pairing between the chiral gold-tethered phosphate and an iminium unit, that provides a rigid, well-defined chiral environment to the key electrophilic intermediate. [ABSTRACT FROM AUTHOR]