Search

We disclose a benzylic C−H oxidative coupling reaction with alcohols that proceeds through a synergistic deprotonation, halogenation and substitution sequence. The combination of tert‐butoxide bases with 2‐halothiophene halogen oxidants enables the first general protocol for generating and using benzyl halides through a deprotonative pathway. In contrast to existing radical‐based methods for C−H functionalization, this process is guided by C−H acidity trends. This gives rise to new synthetic capabilities, including the ability to functionalize diverse methyl(hetero)arenes, tolerance of oxidizable and nucleophilic functional groups, precision site‐selectivity for polyalkylarenes and use of a double C−H etherification process to controllably oxidize methylarenes to benzaldehydes. [ABSTRACT FROM AUTHOR]

The main pathway of the reaction of benzal and benzyl halides with phosphorus(iv) acid esters followed the dehalophosphonyl/phosphinyl(oxylation) course and led to the corresponding carbonyl-containing compounds or benzyl esters. A new reaction between α-chloro ethers and O-alkyl diethylphosphinates was discovered. The reactions of benzyl halides with esters of phosphorus(iv) and orthocarboxylic acids were catalyzed by anhydrous zinc chloride. [ABSTRACT FROM AUTHOR]

The synthesis of a nanocomposite material consisting of Cu nanoparticles encapsulated in halloysite nanotubes (Cu@Hal) was achieved by the reduction of Cu(NO3)2 ⋅ 3H2O with sodium ascorbate/sodium borohydride in an aqueous suspension of trisodium citrate and halloysite. The nanocomposite was found to be an effective heterogeneous catalyst for the multicomponent copper catalyzed azide‐alkyne cycloaddition reaction (CuAAC). A variety of terminal alkynes reacted with benzyl halides and sodium azide in the presence of Cu@Hal in water. In situ formation of the organic azides afforded the corresponding 1,4‐disubstituted 1,2,3‐triazoles regioselectivily, in excellent yields. The catalyst was easily recovered and recycled without loss of activity with low metal leaching. [ABSTRACT FROM AUTHOR]

A simple and commercially feasible route of synthesis of thiols and thioethers was developed using a simple phase transfer catalyst, i.e., Tetra Butyl Ammonium Bromide (TBAB). Sodium hydrogen sulfide (NaSH) is used as a sulfurization agent which is easily available and cost-effective. Thiols are obtained by treating alkyl or benzyl halides with sodium hydrogen sulfide (NaSH) in the presence of a phase transfer catalyst (TBAB) at 10 to 15℃. Thioethers are obtained by benzyl thiols treated with corresponding benzyl halides in the presence of a phase transfer catalyst (TBAB) at 10 to 15℃. Synthesis of thiols and thioethers is achieved by substitution reaction of benzyl or alkyl halides with sulfide in the presence of phase transfer catalyst (TBAB) and monochlorobenzene as a solvent at 10 to 15℃. Milder reaction conditions, excellent yield, shorter reaction time and operational simplicity are the key features of this procedure. [ABSTRACT FROM AUTHOR]

This study introduced a versatile class of indole‐based benzimidazolium salts, offering distinct advantages: (1) the utilization of affordable and easily accessible starting materials; (2) a straightforward and uncomplicated synthesis process; (3) the diversity of the salt should provide fine‐tunability of steric and electronic properties. These salts, employed as N‐heterocyclic carbene (NHC) precursors, were effectively utilized in the Pd‐catalyzed C–C bond formation reactions involving aryl or benzyl halide. The catalytic system, arising from the in situ generation of Pd(OAc)2 and indole‐based benzimidazolium salts, demonstrated remarkable efficiency. It accomplished the synthesis of diarylmethanes via the Suzuki coupling of benzyl chlorides and arylboronic acids in aqueous media with a Pd loading of 0.5 mol%. Furthermore, it successfully achieved the one‐pot sequential Heck/Suzuki coupling reactions with a Pd loading of as low as 0.25 mol%. [ABSTRACT FROM AUTHOR]

Context: Organic halides stand as invaluable reagents with diverse applications in synthetic chemistry and various industrial processes. Despite their utility, concerns arise due to their inherent toxicity. Addressing these apprehensions, hydro-dehalogenation has emerged as a promising strategy involving the replacement of halogen atoms with hydrogen atoms to transform toxic organic halides into hydrocarbons. This study delves into the computational exploration of hydro-dehalogenation reactions of benzyl halide, mediated by frustrated Lewis pairs (FLPs), using density functional theory (DFT). The reactions entail the formation of FLP1 or FLP2 in the presence of TMP or lutidine with B(C6F5)3, respectively. This is followed by heterolytic cleavage of dihydrogen and subsequent reaction with benzyl halides. Non-covalent interaction analysis underscores the significance of π–π stacking and CH–π interactions in stabilizing transition states. Additionally, the activation strain model (ASM) dissects activation energies, revealing the substantial impact of strain energy on reaction barriers. Energy decomposition analysis (EDA) offers insights into the contributions of electrostatic, orbital, and dispersion energies to the overall attractive interaction energy. The investigation extends to hydro-dehalogenation reactions of ethyl halides, uncovering distinct mechanisms and activation barriers. This comprehensive analysis illuminates the intricacies of hydro-dehalogenation reactions, providing valuable insights into their mechanisms and paving the way for future studies in this field. Methods: Geometry optimizations were carried out at the M06-2X/def2-SVP level of theory, which was performed using the Gaussian 16 program. Solvent-corrected single-point energies were also calculated using the polarizable continuum model (PCM) at the PCM(chloroform)-M06-2X/def2-TZVP//M06-2X/def2-SVP level of theory. The Gibbs free energy correction was determined from computations performed at the M06-2X/def2-SVP level of theory. Principal interacting orbital (PIO) analysis was conducted using the NBO 6.0 software. The nature of bonding in the respective transition state (TS) structures was analyzed using atoms-in-molecules (AIM) analyses. Additionally, the presence of non-covalent interactions (NCI) was exemplified using Multiwfn software. [ABSTRACT FROM AUTHOR]

Both aryl and benzyl polybromides have gained significant importance as reactive building blocks in polymer and materials chemistry. Their preparation primarily relies on established synthetic methods using molecular bromine or N-bromosuccinimide, known for their reliability and effectiveness. However, from a sustainability perspective, these methods suffer from the generation of stoichiometric amounts of byproducts and often encounter selectivity troubles. To mitigate these issues, we extended the greener peroxide-bromide halogenation method, initially developed for monobromides, to afford aryl-cored polybromides in high yields. The same method can be employed in two variants modulated by light irradiation. This external switch can be used to selectively trigger side-chain or core halogenation.

In contrast with the well‐established C(sp2)−SCF3 cross‐coupling to forge the Ar−SCF3 bond, the corresponding enantioselective coupling of readily available alkyl electrophiles to forge chiral C(sp3)−SCF3 bond has remained largely unexplored. We herein disclose a copper‐catalyzed enantioselective radical C(sp3)−SCF3 coupling of a range of secondary/tertiary benzyl radicals with the easily available (Me4N)SCF3 reagent. The key to the success lies in the utilization of chiral phosphino‐oxazoline‐derived anionic N,N,P‐ligands through tuning electronic and steric effects for the simultaneous control of the reaction initiation and enantioselectivity. This strategy can successfully realize two types of asymmetric radical reactions, including enantioconvergent C(sp3)−SCF3 cross‐coupling of racemic benzyl halides and three‐component 1,2‐carbotrifluoromethylthiolation of arylated alkenes under mild reaction conditions. It therefore provides a highly flexible platform for the rapid assembly of an array of enantioenriched SCF3‐containing molecules of interest in organic synthesis and medicinal chemistry. [ABSTRACT FROM AUTHOR]

In contrast with the well‐established C(sp2)−SCF3 cross‐coupling to forge the Ar−SCF3 bond, the corresponding enantioselective coupling of readily available alkyl electrophiles to forge chiral C(sp3)−SCF3 bond has remained largely unexplored. We herein disclose a copper‐catalyzed enantioselective radical C(sp3)−SCF3 coupling of a range of secondary/tertiary benzyl radicals with the easily available (Me4N)SCF3 reagent. The key to the success lies in the utilization of chiral phosphino‐oxazoline‐derived anionic N,N,P‐ligands through tuning electronic and steric effects for the simultaneous control of the reaction initiation and enantioselectivity. This strategy can successfully realize two types of asymmetric radical reactions, including enantioconvergent C(sp3)−SCF3 cross‐coupling of racemic benzyl halides and three‐component 1,2‐carbotrifluoromethylthiolation of arylated alkenes under mild reaction conditions. It therefore provides a highly flexible platform for the rapid assembly of an array of enantioenriched SCF3‐containing molecules of interest in organic synthesis and medicinal chemistry. [ABSTRACT FROM AUTHOR]

In contrast with the well‐established C(sp2)−SCF3 cross‐coupling to forge the Ar−SCF3 bond, the corresponding enantioselective coupling of readily available alkyl electrophiles to forge chiral C(sp3)−SCF3 bond has remained largely unexplored. We herein disclose a copper‐catalyzed enantioselective radical C(sp3)−SCF3 coupling of a range of secondary/tertiary benzyl radicals with the easily available (Me4N)SCF3 reagent. The key to the success lies in the utilization of chiral phosphino‐oxazoline‐derived anionic N,N,P‐ligands through tuning electronic and steric effects for the simultaneous control of the reaction initiation and enantioselectivity. This strategy can successfully realize two types of asymmetric radical reactions, including enantioconvergent C(sp3)−SCF3 cross‐coupling of racemic benzyl halides and three‐component 1,2‐carbotrifluoromethylthiolation of arylated alkenes under mild reaction conditions. It therefore provides a highly flexible platform for the rapid assembly of an array of enantioenriched SCF3‐containing molecules of interest in organic synthesis and medicinal chemistry. [ABSTRACT FROM AUTHOR]

In contrast with the well‐established C(sp2)−SCF3 cross‐coupling to forge the Ar−SCF3 bond, the corresponding enantioselective coupling of readily available alkyl electrophiles to forge chiral C(sp3)−SCF3 bond has remained largely unexplored. We herein disclose a copper‐catalyzed enantioselective radical C(sp3)−SCF3 coupling of a range of secondary/tertiary benzyl radicals with the easily available (Me4N)SCF3 reagent. The key to the success lies in the utilization of chiral phosphino‐oxazoline‐derived anionic N,N,P‐ligands through tuning electronic and steric effects for the simultaneous control of the reaction initiation and enantioselectivity. This strategy can successfully realize two types of asymmetric radical reactions, including enantioconvergent C(sp3)−SCF3 cross‐coupling of racemic benzyl halides and three‐component 1,2‐carbotrifluoromethylthiolation of arylated alkenes under mild reaction conditions. It therefore provides a highly flexible platform for the rapid assembly of an array of enantioenriched SCF3‐containing molecules of interest in organic synthesis and medicinal chemistry. [ABSTRACT FROM AUTHOR]

The alkylation of ethyl 2-aryl-1-hydroxy-4-methyl-1H-imidazole-5-carboxylates with substituted benzyl halides resulted in the selective formation of O-alkoxy derivatives. N-Alkylation products (1-alkylimidazole 3-oxides) were obtained by the condensation reaction from acyclic starting compounds. In the presence of the 2-hydroxyphenyl substituent in the 2-position of the imidazole ring, selective monoalkylation involving the hydroxyl substituent on the imidazole nitrogen takes place. [ABSTRACT FROM AUTHOR]

A straightforward and effective strategy for the synthesis of novel 7-cyano-4-imino-3-phenyl-6-(pyrrolidin-1-yl)-2-substituted-3,4-dihydroselenopheno[3,2-d]pyrimidines have been accomplished through a base-promoted cascade addition/cyclization sequence employing phenyl isothiocyanate followed by the S-alkylation of the obtained fused Se-containing heterocyclic framework with various alkyl halides. Free radical scavenging activity of the synthesized selenium-containing structures was studied against DPPH, as well. Antioxidant activities as IC50 values were ranged from 12.19 to 91.08 µM. Unfused 3-amino-2,4-dicyano-5-(pyrrolidin-1-yl)selenophene was much more powerful antioxidant agent than ascorbic acid. Moreover, the promising antioxidant potentials were observed with selenopheno[3,2-d]pyrimidines. Taking into account the best antioxidant activity of S-benzylated derivative amongst pyrimidine-fused heterocycles and significant relationship between antioxidant activity of compounds and many of their biological potencies, using benzyl halides bearing electron donating groups on phenyl ring can probably improve their antioxidant capacities to make them more effective anti-cancer, anti-diabetic, anti-inflammatory and anti-neurodegenerative agents. [ABSTRACT FROM AUTHOR]

A visible‐light‐triggered silyloxymethylation of aryl halides has been developed by the merger of photoredox and transition metal catalysis. Under the Ru/Ni dual catalytic conditions, sodium tert‐butyl‐dimethylsilyloxymethanesulfinate (SOMS) undergoes facile extrusion of sulfur dioxide to engender a silyloxymethyl radical that engages in the cross‐coupling with a range of aryl halides to produce benzyl silyl ether derivatives. The protocol is also effective with alkenyl halides and triflates, thus offering an efficient synthetic approach to the silyl‐protected allylic alcohols. [ABSTRACT FROM AUTHOR]

A new organic-functionalized Cu-based Anderson-type polyoxomolybdate, namely (C7H15N4)2[Na(H2O)4]2[C6H12CuMo6N2O24]·2(H2O) (CuII-POM), was synthesized via a simple one-pot reaction and subsequently characterized using a range of analytical and spectral techniques. Structural investigation by single crystal X-ray diffraction analysis revealed that the polyanion component of the synthesized compound (i.e. [C6H12CuMo6N2O24]4−) possesses a δ-isomer Anderson-type structure, which is surrounded by four lattice water molecules and four [C7H15N4–NaH15(H2O)8]4+ cations in the crystal packing arrangement. The resulting double-sided tris-functionalized Anderson-type compound can function as highly effective heterogeneous photocatalysts for the copper(I)-catalyzed Huisgen azide-alkyne cycloaddition (Cu-AAC) reaction of terminal alkyne, benzyl halides, and sodium azide (acts as the azidonation and reducing agent) in aqueous media. Ultraviolet light irradiation enhances the catalytic activity of CuII-POM ~ 4.4 times of the "off" situation under reaction conditions of 0.00239 mmol cat., 80 °C, 8 h, 2 mL H2O, So that the isolated yields for the AAC reaction involving a variety of terminal alkynes and benzyl halides using the CuII-POM catalyst ranged between 19–97%. The current study is the first report about using an efficient and economical Cu(II)-POM/UV/NaN3 catalytic system in the Cu-AAC reaction and reveals its significant potential for applying to other Cu(I)-catalyzed reactions. [ABSTRACT FROM AUTHOR]

SP 1 sp H NMR (400 MHz, CDCl SB 3 sb ): = 12.46 (s, 1 H), 9.12-9.10 (m, 2 H), 8.84 (dd, I J i SB 1 sb = 4.2, I J i SB 2 sb = 1.7 Hz, 1 H), 8.14-8.10 (m, 2 H), 7.62-7.58 (m, 1 H), 7.49 (dd, I J i SB 1 sb = 8.2, I J i SB 2 sb = 1.1 Hz, 1 H), 7.42-7.39 (m, 2 H), 7.32 (d, I J i = 8.1 Hz, 1 H), 7.28-7.24 (m, 1 H), 6.83 (s, 1 H), 4.29-4.23 (m, 5 H), 1.43 (t, I J i = 7.3 Hz, 3 H). SP 1 sp H NMR (400 MHz, CDCl SB 3 sb ): = 7.98 (d, I J i = 7.7 Hz, 1 H), 7.94 (dd, I J i SB 1 sb = 8.0, I J i SB 2 sb = 0.9 Hz, 1 H), 7.40-7.36 (m, 1 H), 7.33 (d, I J i = 7.8 Hz, 1 H), 7.21-7.17 (m, 1 H), 6.84-6.82 (m, 2 H), 4.27 (q, I J i = 7.2 Hz, 2 H), 3.91 (s, 3 H), 1.39 (t, I J i = 7.2 Hz, 3 H). SP 1 sp H NMR (400 MHz, CDCl SB 3 sb ): = 8.64 (s, 1 H), 8.03 (d, I J i = 7.7 Hz, 1 H), 7.41-7.37 (m, 1 H), 7.32 (d, I J i = 8.1 Hz, 1 H), 7.19-7.16 (m, 1 H), 7.12 (s, 1 H), 4.34 (q, I J i = 7.2 Hz, 2 H), 4.28 (q, I J i = 7.2 Hz, 2 H), 3.10 (t, I J i = 8.0 Hz, 2 H), 1.65-1.57 (m, 2 H), 1.40-1.35 (m, 8 H), 1.28-1.19 (m, 16 H), 0.79 (t, I J i = 6.5 Hz, 3 H). SP 1 sp H NMR (400 MHz, CDCl SB 3 sb ): = 8.70 (s, 1 H), 8.11 (d, I J i = 7.7 Hz, 1 H), 7.96-7.96 (m, 1 H), 7.93-7.90 (m, 1 H), 7.56-7.53 (m, 1 H), 7.49-7.43 (m, 2 H), 7.39 (d, I J i = 8.2 Hz, 1 H), 7.27-7.22 (m, 2 H), 4.32 (q, I J i = 7.3 Hz, 2 H), 4.08 (q, I J i = 7.2 Hz, 2 H), 2.58 (s, 3 H), 1.38 (t, I J i = 7.2 Hz, 3 H), 1.00 (t, I J i = 7.1 Hz, 3 H). [Extracted from the article]

In this research, a nano-inorganic composite of CuO/NiO is prepared by co-precipitation method as an efficient recyclable nanocatalyst for the regioselective synthesis of 1,4-disubstituted-1,2,3-triazoles in water. The catalyst was characterized by several techniques such as the field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS), x-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), x-ray fluorescence, inductively coupled plasma atomic emission spectroscopy (ICP-OES), and brunauer-emmett-teller (BET) surface area analysis. The regioselective synthesis of 1,4-disubstituted-1,2,3-triazoles was carried out from reaction of various benzyl halides or alkyl halides with phenyl acetylene and sodium azide in water under reflux condition in high yields. The CuO/NiO nanocatalyst can be simply recovered and reused 6 runs without a significant slight in activity. [ABSTRACT FROM AUTHOR]

The chemical stability of the electrogenerated radical anion of N‐(aminobenzyl) phthalimide 1 in aprotic organic media at room temperature is reported in this work. The redox couples 1/1⋅− and its imine precursor 2/2⋅− can carry out reductive redox catalysis of benzyl or allyl halides indirectly. This reaction gives easy access to reactive alkyl radicals, which in the presence of diethyl fumarate yields 2‐benzylsuccinate diethyl ester in moderate yields; this reaction is unattainable by direct electrochemical reduction. Spin density calculations at the DFT level of theory showed that the spin density of 1⋅− and 2⋅− is located on the phtalimide ring, and a dimeric association was evidenced (Eint=23.47 kcal/mol and Eint=80.42 kcal/mol respectively), via π−π stacking interactions. The redox mediators presented here showed good functional group selectivity, redox potential tunability and easy preparation from readily available commercial materials with excellent yields. [ABSTRACT FROM AUTHOR]

The direct N‐alkylation reactions of ambident 3,5‐substituted 4‐nitroso‐1H‐pyrazoles are described for the first time. An efficient method of the 4‐nitroso‐1H‐pyrazoles and their sodium alkyl‐, allyl‐ salts regioselective N‐alkylation by benzyl halides, halocarboxylic acids esters, and related bifunctional alkylating agents is established with the use of superbasic conditions or reflux in acetone. A series of new N‐functionalized nitrosopyrazoles and bis(4‐nitrosopyrazole) compounds is successfully obtained with a yield of up to 85 %. Using quantum‐chemical calculations, it is shown that in terms of kinetics and thermodynamics, the N‐alkylation of the considered pyrazoles is a more advantageous process than O‐alkylation. [ABSTRACT FROM AUTHOR]

The synthesis of a series of new organophosphorane bis-ylide ligands is described. Upon their deprotonation, the stabilization of the ylide α-carbanion is achieved through the negative charge delocalization either over the π-system of the α-aryl groups bonded to carbanionic centers or over the {Cp}-type aromatic system in the case when the α-carbanion is involved in this system. The dibenzyl ylides [Ph2P(=CHAr)(CH2Ar)] were synthesized in situ starting from Ph2PLi and 2 equiv. of benzyl halides that significantly increased the yields of the target compounds. Ligands of the fluorenylidene, indenylidene, and cyclopentadienylidene types were synthesized in high yields. π-Stabilized organo-phosphorane ligands are readily metalated with potassium hydride and sodium amide to give the corresponding salts as solvates with THF. The reaction of 9-(diphenylphosphino)-fluorenide, Li[Ph2PC13H8], with Ph2PCl afforded the gem-bis(phosphine) ligand [9,9-(Ph2P)2C13H8] that readily gave the corresponding palladium complex [{κ-P, P-(Ph2P)2C13H8}PdCl2] in high yield. [ABSTRACT FROM AUTHOR]

An ultrasound-assisted simple, easy and straightforward method for the synthesis of α-aminophosphonates has been developed via Kornblum/Kabachnik-fields reaction. The method involves in situ generation of an aldehyde intermediate from benzyl halides via oxidative dehalogenation followed by coupling with aryl amine and trialkyl phosphite in a one-pot three component manner under ultrasonic irradiations. The developed method is compatible with various functionalities and the desired products are obtained in good to excellent yield under mild conditions. [ABSTRACT FROM AUTHOR]

Aryl thioethers and their derivatives constitute an important class of organic compounds that play an important role in the synthesis of natural products, and pharmaceutically and biologically active molecules. Hence, the formation of C–S bonds is a very important process in organic synthesis. The cross-coupling reaction is one of the most popular and powerful tools for C–S bond formation. This study presents an odourless and ligand-free protocol for the synthesis of aryl thioethers via a CoFe2O4 NP catalysed coupling reaction between benzyl halides and aryl halides in the presence of thiourea as a sulphur source. CoFe2O4 NPs have been synthesized by a hydrothermal process at 180 °C in the absence of any added stabilizer. The synthesized CoFe2O4 NPs are spherical with sizes varying from 7 to 15 nm and possess cubic structures. They exhibit ferromagnetic behaviour at room temperature while above the blocking temperature, TB, the material shows superparamagnetic behaviour. This behaviour makes the catalyst magnetically separable and reusable up to 7th cycle without much loss of their catalytic activity. The protocol can be expanded to a wide array of substituted aryl halides and substituted benzyl halides with moderate to excellent yields. [ABSTRACT FROM AUTHOR]

A convenient and effective method for the construction of C−S bond under transition‐metal free conditions was reported. Thus, diverse thiocarbamide esters could be smoothly obtained in moderate to good yields from inexpensive and readily available starting materials, such as phenyl isothiocyanate, alcohols and benzyl halides. This method features mild conditions, easy operation, short reaction time and broad substrate scopes, providing a facile and convenient strategy for the preparation of some compounds with potential biological activities. [ABSTRACT FROM AUTHOR]

A direct and convenient method for the palladium‐catalyzed reductive cross‐coupling of aryl iodides or alkenyl bromides and secondary benzyl halides under ambient CO pressure to generate a diverse array of aryl/alkenyl alkyl ketones has been developed. This strategy successfully achieves a three‐component carbonylative reaction with Zn as the reducing agent for C−C bond formation, overcoming the well‐known homocoupling of aryl or alkenyl halides, direct cross‐coupling between two different electrophiles and other carbonylative coupling reactions. In addition, this method avoids use of preformed organometallic nucleophiles, such as organo‐magnesium, zinc and boron reagents. This approach enables the construction of valuable aryl alkyl/alkenyl ketone derivatives (60 examples, 56–95% yields). Reactivity studies indicate that in situ formed benzylic zinc reagents are intermediates in the catalytic system. [ABSTRACT FROM AUTHOR]

Denitrification. In their Research Article (e202408457), Yunho Lee et al. report an innovative NOx pollutant remediation and upcycling approach via organonickel pincer catalysis. Ni‐nitrosyl species obtained from sequential nitrate deoxygenation undergo C−N coupling with various benzyl and alkyl halides...By Sudakar Padmanaban; Jeewon Chun; Youngseob Lee; Kyung‐Bin Cho; Jonghoon Choi and Yunho LeeReported by Author; Author; Author; Author; Author; Author [Extracted from the article]

This document, titled "Titelbild: Unraveling the Origin of Multichannel Circularly Polarized Luminescence in a Pyrene-Functionalized Topologically Chiral [2]Catenane," is a research article published in Angewandte Chemie. The article discusses the use of time-resolved circularly polarized luminescence (TRCPL) spectroscopy and transient absorption (TA) spectroscopy to differentiate between chiroptical signals originating from topological or Euclidean chirality in a topologically chiral [2]catenane. Another research article by Yunhoo Lee et al. presents an innovative approach to remediating and upcycling NOx pollutants using organonickel pincer catalysis. Xiaoping Xue, Ruixian Deng et al. present a symmetric-anion-mediated dynamic kinetic asymmetric Knoevenagel reaction for accessing axial chiral atropisomers in their research article. Shujun Li, Zhijun Chen, Bernd Strehmel et al. demonstrate the performance of a new material produced by confinement of cellulose-based carbon dots in their research article, which functions as a long afterglow emitter and photocatalyst. Lastly, Ru-Jia Yu, Yi-Tao Long et al. report on the development of a synapse-mimicking nanopipette method for electrochemically monitoring single vesicle dynamics induced by lipid-tau interactions in their communication. [Extracted from the article]

This article, published in Angewandte Chemie International Edition, discusses various research articles in the field of chemistry. One article focuses on differentiating chiroptical signals in a topologically chiral [2]catenane using spectroscopy techniques. Another article explores an innovative approach to remediate and upcycle NOx pollutants using organonickel pincer catalysis. A third article presents a method for accessing chiral atropisomers through a dynamic kinetic asymmetric reaction. Additionally, the article mentions research on a new material that functions as a long afterglow emitter and photocatalyst, as well as a method for electrochemically monitoring single vesicle dynamics. [Extracted from the article]

Herein, we report the efficient synthesis of copper(II) phthalocyanines in the presence of DBU as a strong base. These synthesized copper(II) phthalocyanines are utilized as a catalyst for the click reactions of sensitive compounds including metal-free porphyrins under mild reaction conditions at room temperature. Further, we have developed a one-pot procedure for the click reactions of benzyl halides with different alkynes in good to excellent yields. The reaction proceeds at room temperature to 40 °C and gives 83–99% of products. The reactions are carried out in DMSO solvent. The present reaction condition offers copper(II) phthalocyanines as an efficient and convenient catalyst for different electron-rich and electron-deficient substrates including macrocyclic compounds. Electron-deficient substrates and less steric substrates provide a better result. The catalyst is easily separated from the reaction by a simple filtration technique and is reused up to 5 times without significant loss of its catalytic activity. [ABSTRACT FROM AUTHOR]

Heterogeneous photocatalysis offers an eco-friendly platform for selective C–C coupling of benzyl halides via hydro-dehalogenation by employing alcohols as the hydrogen donor, yet the reaction rate under visible light irradiation needs significant enhancement for applications. This calls for a designed and affordable photocatalyst with optimized adsorption and kinetics for the selective conversion of reactants and intermediates. Here we demonstrate that choosing an optimal metal as cocatalyst supported on the graphitic carbon nitride (gCN) photocatalyst, the adsorption of benzyl halide, the activation of the C–X bond, and the removal kinetics of photogenerated active halogen species can be manipulated to tune the generation rate of bibenzyl. In comparison with Pd and Cu, Ni supported on gCN presents a moderate adsorption of benzyl halide, a fast C–X dissociation rate, and a rapid removal of active halogen anions, thus achieving a 13-fold enhancement for C–C coupling of halogenated arenes under visible light irradiation. Such high performance also makes it a promising photocatalyst for scalable synthesis of value-added bibenzyls in a flow system. [ABSTRACT FROM AUTHOR]

An odorless and efficient protocol for the synthesis of benzyl phenyl sulfides is reported. Starting from environmentally friendly phenyl dithiocarbamates and commercially available benzyl halides as starting materials, the target compounds (benzyl phenyl sulfides) could be obtained smoothly and easily by using copper salt as catalyst and Cs2 CO3 as base. This method features ligand/additive-free, the use of readily available starting materials, inexpensive catalysts, and good substrate suitability, illustrating its potentially synthetic value for the convenient preparation of some biologically active molecules. [ABSTRACT FROM AUTHOR]

A CuI-catalyzed condensation reaction between alcohols, alkyl halides, and Na2S2O3 leading to structurally diverse thioethers is reported. A variety of alkyl halides and electron-rich benzyl alcohols were employed successfully in the presence of 5 mol% CuI in PEG-200 at 110 °C. The method does not require any ligands or additives. The unsymmetrical thioethers were achieved in good to excellent yields within appropriate reaction times. [ABSTRACT FROM AUTHOR]

In this study, acetovanillone-derived novel benzyl ethers were synthesized as target compounds. For the synthesis of these target compounds, ketone derivatives (3a–b) were synthesized as the starting compounds. Compounds 4a–b, which are alcohol derivatives, were then synthesized from the reduction of these ketone derivatives. In the last stage of the synthesis study, benzyl ether derivatives (6a–h, 7a–h), the target compounds containing acetovanillone, were synthesized from the reaction of the alcohol derivatives (4a–b) with various benzyl halides (5a–h). The structures of the synthesized compounds were characterized by various spectroscopic methods (FT-IR, 1H NMR, 13C NMR, mass spectrometry, and elemental analysis). In vitro antileishmanial and antibacterial activity tests were then performed for all synthesized compounds. Biological activity tests showed that while only a few of the compounds had antileishmanial activity, most had antibacterial activity. In addition, the ADME parameters, pharmacokinetic properties, and drug-like nature of all compounds were theoretically investigated using the SwissADME webserver. Finally, molecular docking simulations were carried out to support in vitro investigations and evaluate the inhibition effect of the synthesized compounds on the 3IW2 (Mycobacterium tuberculosis (Mtb) Cyp125; Pdb ID: 3IW2) receptor structure. Also, possible binding sites of some compounds with high affinity to Mtb Cyp125 according to docking results were identified. [ABSTRACT FROM AUTHOR]

Hydrogen peroxide, a cheap and easily available green oxidant, can not only produce oxygen, but also produce hydroxyl radical by homogenization under the catalysis of metal. Toluene and benzyl halide can be oxidized to benzaldehyde by hydrogen peroxide and participate in the reaction with 2‐aminobenzylamine. Through the construction of C−N bond, a series of quinazoline derivatives were synthesized. This reaction allows a broad range of substrates as well as good functional group compatibility. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: A new set of stereochemically diverse phosphino‐oxazoline ligands derived from simple L‐amino acids and 2‐(diphenylphosphaneyl)benzoic acid were developed. Those mono anionic tridentated N,N,P‐ligands promote the Cu‐catalyzed enantioselective radical coupling of terminal alkynes with a broad range of benzylic halides including benzo‐fused cyclic α‐halides and α‐silyl benzyl halides in high yield and excellent enantioselectivity under mild reaction conditions. With multi distinct sites for structural modification, a diverse pool of chiral N,N,P‐ligands is readily accessed, allowing for rapid optimization of the ligand structure for a specific substrate. Notably, the enantioselective alkynlylation of benzylic halides bonds in benzo‐cyclic molecules has also been realized for the first time. [ABSTRACT FROM AUTHOR]

Starting with fluorinated benzylamines, a series of 2-unsubstituted imidazole N-oxides was prepared and subsequently deoxygenated in order to prepare the corresponding imidazoles. The latter were treated with benzyl halides yielding imidazolium salts, which are considered fluorinated analogues of naturally occurring imidazolium alkaloids known as lepidilines A and C. A second series of oxa-lepidiline analogues was obtained by O-benzylation of the initially synthetized imidazole N-oxides. Both series of imidazolium salts were tested as anticancer and antiviral agents. The obtained results demonstrated that the introduction of a fluorine atom, fluoroalkyl or fluoroalkoxy substituents (F, CF3 or OCF3) amplifies cytotoxic properties, whereas the cytotoxicity of some fluorinated lepidilines is promising in the context of drug discovery. All studied compounds revealed a lack of antiviral activity against the investigated viruses in the nontoxic concentrations. [ABSTRACT FROM AUTHOR]

A green mesoporous catalyst was prepared by copper immobilization onto L-phenylalanine (L-Phe), and it was studied using different analytical methods, including FT-IR, XRD, FE-SEM, EDX, BET, TGA, DSC, and ICP analysis. Using sodium azide, phenylacetylene, benzyl or alkyl halides, and a nanocatalyst, the CuAAC reaction has been effectively utilized to produce 1,2,3-triazoles with regioselective efficiency. The main advantages of the current approach are the easy recyclability of the catalyst, short reaction time, low cost, simple preparation, and high yield. Furthermore, the (L-Phe)-CuO showed antimicrobial properties. [ABSTRACT FROM AUTHOR]

An efficient Pd‐catalyzed one‐pot desulfinative cross‐coupling to access medicinally relevant di(hetero)arylmethanes is reported. The method is reductant‐free, and involves a sulfinate transfer reagent and a Pd‐catalyst mediating the union of two electrophilic coupling partners; a (hetero)aryl halide and a benzyl halide. We establish for the first time that benzyl sulfinates, generated in situ, undergo efficient Pd‐catalyzed desulfinative cross‐coupling with (hetero)aryl halides to generate di(hetero)arylmethanes. The reaction can be extended to benzylic pseudohalides derived from benzyl alcohols. The reactions are straightforward to perform and scalable, and all reaction components are commercially available. [ABSTRACT FROM AUTHOR]

A new route to synthesis of various mono‐N‐substituted hydrazines and hydrazides by involving in a new C−N bond formation by using N‐amino‐1,8‐naphthalimide as a regenerated precursor was invented. Aniline and phenylhydrazines are reproduced upon reacting these individually with 1,8‐naphthalic anhydride followed by hydrazinolysis. The practicality and simplicity of this C−N dihalo alkanes; developed a synthon for bond formation protocol was exemplified to various hydrazines and hydrazides. N‐amino‐1,8‐naphthalimide is suitable synthon for transformation for selective formation of mono‐substituted hydrazine and hydrazide derivatives. Those are selective mono‐amidation of hydrazine with acid halides; mono‐N‐substituted hydrazones from aldehydes; synthesis of N‐aminoazacycloalkanes from acetohydrazide scaffold and inserted to hydroxy derivatives; distinct synthesis of N,N‐dibenzylhydrazines and N‐benzylhydrazines from benzyl halides; synthesis of N‐amino‐amino acids from α‐halo esters. Ecofriendly reagent N‐amino‐1,8‐naphthalimide was regenerated with good yields by the hydrazinolysis in all procedures. [ABSTRACT FROM AUTHOR]

Transition‐metal catalyzed multi‐component reactions have captured the attention of researchers in organic synthesis and drug synthesis due to their advantages of simple operation, easy availability of raw materials and without separation of intermediates. Among the multi‐component reactions, the three‐component processes have been developed into effective organic procedures. This personal account reviews our and other group's studies on the development of three‐component coupling reaction for the rapid construction of two new chemical bonds simultaneously via benzylpalladium intermediates. Catalyst‐switched three‐component reactions of benzyl halides, activated olefins, and allyltributylstannane were successfully conducted to produce the corresponding benzylallylation products. Activation and conversion of carbon monoxide and carbon dioxide via π‐benzylpalladium intermediates provide access to a wide range of unsaturated ketones and esters with excellent functional group tolerance. Meanwhile, other methods to produce benzylpalladium intermediates, including Heck insertion of alkenes into arylpalladium complexes, the oxidative addition of benzyl carbonate to palladium complexes and palladium−carbene migratory insertion, were also highlighted. [ABSTRACT FROM AUTHOR]

We report a Ni‐catalyzed regioselective arylbenzylation of alkenylarenes with benzyl halides and arylzinc reagents. The reaction furnishes differently substituted 1,1,3‐triarylpropyl structures that are reminiscent of the cores of oligoresveratrol natural products. The reaction is also compatible for the coupling of internal alkenes, secondary benzyl halides and variously substituted arylzinc reagents. Kinetic studies reveal that the reaction proceeds with a rate‐limiting single‐electron‐transfer process and is autocatalyzed by in‐situ‐generated ZnX2. The reaction rate is amplified by a factor of three through autocatalysis upon addition of ZnX2. [ABSTRACT FROM AUTHOR]

We report a Ni‐catalyzed regioselective arylbenzylation of alkenylarenes with benzyl halides and arylzinc reagents. The reaction furnishes differently substituted 1,1,3‐triarylpropyl structures that are reminiscent of the cores of oligoresveratrol natural products. The reaction is also compatible for the coupling of internal alkenes, secondary benzyl halides and variously substituted arylzinc reagents. Kinetic studies reveal that the reaction proceeds with a rate‐limiting single‐electron‐transfer process and is autocatalyzed by in‐situ‐generated ZnX2. The reaction rate is amplified by a factor of three through autocatalysis upon addition of ZnX2. [ABSTRACT FROM AUTHOR]

We report a Ni‐catalyzed regioselective arylbenzylation of alkenylarenes with benzyl halides and arylzinc reagents. The reaction furnishes differently substituted 1,1,3‐triarylpropyl structures that are reminiscent of the cores of oligoresveratrol natural products. The reaction is also compatible for the coupling of internal alkenes, secondary benzyl halides and variously substituted arylzinc reagents. Kinetic studies reveal that the reaction proceeds with a rate‐limiting single‐electron‐transfer process and is autocatalyzed by in‐situ‐generated ZnX2. The reaction rate is amplified by a factor of three through autocatalysis upon addition of ZnX2. [ABSTRACT FROM AUTHOR]

We report a Ni‐catalyzed regioselective arylbenzylation of alkenylarenes with benzyl halides and arylzinc reagents. The reaction furnishes differently substituted 1,1,3‐triarylpropyl structures that are reminiscent of the cores of oligoresveratrol natural products. The reaction is also compatible for the coupling of internal alkenes, secondary benzyl halides and variously substituted arylzinc reagents. Kinetic studies reveal that the reaction proceeds with a rate‐limiting single‐electron‐transfer process and is autocatalyzed by in‐situ‐generated ZnX2. The reaction rate is amplified by a factor of three through autocatalysis upon addition of ZnX2. [ABSTRACT FROM AUTHOR]

Cu2+‐crosslinked carboxymethylcellulose/diatomite composite beads (CuII@CMC/DE) were prepared in simple and efficient way using ionic crosslinking techniques. In CuII@CMC/DE beads, diatomite serves as a reinforcing filler, and divalent copper cation acts as crosslinking agent. The chemical structure and morphology of as‐fabricated CuII@CMC/DE beads were well characterized using various techniques such as ICP, FT‐IR, XRD, SEM, EDS, elemental mapping, TEM, XPS, and TGA. The CuII@CMC/DE beads exerted superior catalytic performance in CuAAC reactions of benzyl halides, sodium azide, and alkynes to yield regioselected 1,4‐disubstitued‐1,2,3‐triazoles in excellent yields under green conditions. In these resultant catalytic composite beads, Cu2+ was used not only as a crosslinking agent but also as a metal catalyst for CuAAC reaction. The composite beads can be easily separated by filter and reused at least four times without any significant decrease on its activity and selectivity. [ABSTRACT FROM AUTHOR]

An efficient and metal‐free methodology for the oxidation of benzyl halides to benzoic acids using an inexpensive and green oxidant (TBHP) in aqueous basic medium has been developed. This protocol offers an excellent way to avoid adding catalysts and involves the use of an in‐situ generated halide ion as catalyst. It is also the first report on the oxidation of benzyl iodides to benzoic acids. A series of carboxylic acids were prepared from benzyl halides in high yields under mild reaction conditions by this method which does not require chromatographic purification. Gram scale reactions for the synthesis of the carboxylic acids in good yields have been successfully carried out using benzyl chloride, bromide and iodide. As an industrial application, the synthesis of a key monomer used for the synthesis of polyethylene terephthalate (PET), i. e. terephthalic acid (PTA), has also been accomplished in good yields. [ABSTRACT FROM AUTHOR]

A pseudo-dearomatized PN³P*Rh-CO complex reacts with various alkyl/benzyl halides to furnish a series of secondgeneration PN³P-pincer carbonyl complexes via the ligand postmodification strategy. These synthesized complexes were fully characterized by NMR, FTIR, HRMS, and single-crystal X-ray crystallography. A plausible mechanism for the formation of 2nd-generation PN³P complexes was proposed based on the isolation of the minor dialkylated products. [ABSTRACT FROM AUTHOR]

Galactose oxidase (E.C. 1.1.3.9) is an extracellular oxidoreductase enzyme containing Cu(I) which is produced by some fungi like Fusarium species. The enzyme catalyzes the selective oxidation of primary alcohols like galactose. In this study, a heterogeneous enzymatic system for click reaction was prepared. The most important advantage of the heterogeneous catalyst is the ease of separation and their possible reusability. Therefore, galactose oxidase was immobilized by entrapment; for this purpose, alginate polysaccharide beads with different diameters were synthesized and galactose oxidase was immobilized into them to obtain galactose oxidase-bead (GO-Bead). Next, the catalytic activity of galactose oxidase-beads was examined in the one-pot synthesis of 1,4-disubstituted 1,2,3-triazoles via click reaction comprising diversely benzyl halides, sodium azide and different alkynes in aqueous medium which need Cu(I) for their performance. The catalyst was conventionally recovered and effectively reused in several runs with no appreciable decrease in its catalytic activity. [ABSTRACT FROM AUTHOR]

Here we report the synthesis of covalent triazine frameworks (CTFs) using benzyl halide monomers which are more cost-effective and with higher availability than previous ones. The resulting CTFs were successfully applied for efficient photocatalytic reforming of glucose for the first time, with a high hydrogen evolution rate up to 330 μmol g−1 h−1 under pH = 12. This work presented a new way to synthesize CTFs and further exhibited their potential applications in photocatalytic biomass reforming. [ABSTRACT FROM AUTHOR]

Transition‐metal mediated activation of inert chemical bonds is an ongoing topic in homogeneous catalysis. In view of the abundance and accessibility of alkylarenes and benzylamines, the use of them as benzyl source in catalytic benzylation reactions via benzylic C—H and C—N bond activation is highly desirable. Indeed, compared with the traditional approaches with benzyl halide as the substrates, benzylation reactions via C—H and C—N bond cleavage provide more efficient, atom‐economic strategies to access myriads of synthetically important molecules. In this account, our group's efforts on catalytic benzylation reactions via directed C—H activation, nondirected C—H activation and C—N bond activation are summarized. What is the most favorite and original chemistry developed in your research group? Palladium‐catalyzed aminal chemistry. How do you supervise your students? Discuss with my students and encourage them to think about where the scientific problem is. What is the most important personality for scientific research? Honesty, curiosity and passion. What are your hobbies? Reading and playing badminton. Who influences you mostly in your life? My parents, who always inspire me to go forward. What is your favorite journal(s)? Journals that fairly review the manuscripts and publish inspiring, innovative research results. [ABSTRACT FROM AUTHOR]