Search

In this article, initially, the TCTCl (DiPrAEA)2 ligand was synthesized and characterized by Fourier transform infrared (FT‐IR), X‐ray crystallography, 1H‐ and 13C‐NMR spectroscopy, and elemental analysis. The crystallographic structure data for the ligand has been deposited at the Cambridge Crystallographic Data Centre (CCDC No. 2282732). Then, using of this novel multidentate ligand, a novel and stable copper (II) nanocatalyst complex was synthesized by anchoring copper (II) acetate onto the core‐shell surface (Fe3O4@SiO2) via the novel multidentate ligand TCTCl (DiPrAEA)2. The successful synthesis of the Fe3O4@SiO2‐NH‐TCT (DiPrAEA)2‐Cu (II) nanocatalyst was confirmed by employing physicochemical techniques such as FT‐IR, X‐ray diffraction, ultraviolet‐visible, thermogravimetric analysis, X‐ray photoelectron spectroscopy, Brunauer–Emmett–Teller, energy‐dispersive X‐ray, dynamic light scattering, inductively coupled plasma, transmission electron microscopy, field emission scanning electron microscopy, and vibrating sample magnetometer. Subsequently, this novel copper (II) nanomagnetic complex was evaluated as an efficient, reusable, and novel catalyst for the formation of C‐N bonds via the Ullmann coupling reaction of aryl halides and nitrogen‐containing compounds. The influence of this novel TCTCl (DiPrAEA)2 ligand on the reactivity and stability of the nanomagnetic copper complex was visible in the Ullmann reaction, which resulted in rapid reaction times and excellent yields, and seven times reusability. [ABSTRACT FROM AUTHOR]

Herein, a novel magnetic mesoporous silica nanocomposite with a core–shell structure modified with IL/Cu complex (MMS@IL/Cu) is prepared through the template-directed hydrolysis of tetramethyl orthosilicate (TMOS) over Fe3O4@RF composite followed by grafting of propyl-imidazolium chloride/copper complex. The MMS@IL/Cu nanocomposite was characterized by PXRD, FT-IR, TGA, VSM, EDX, SEM and TEM techniques. The MMS@IL/Cu was employed as a robust nanocatalyst to successfully promote the Chan-Lam coupling reaction in EtOH at 50 °C. High yields of the desired products were obtained within a relatively short time. The designed magnetic catalyst could retain its high efficiency for at least eight runs under applied conditions. [ABSTRACT FROM AUTHOR]

An efficient method for N-arylation and N-N bond formation has been developed using an innoxious reaction medium, γ-valerolactone (GVL), as both a solvent and a ligand. The strategy involves utilizing CuI as a catalyst under conditions free of external ligands and bases. Various aldehyde and amine derivatives with different functional groups were investigated, resulting in the production of 2-aryl-2H-indazole compounds with yields ranging from 75% to 93%. This study highlights the effectiveness of GVL, a solvent derived from biomass, as a reaction medium and ligand in a multicomponent reaction. [ABSTRACT FROM AUTHOR]

An efficient transamidation process has been described under solvent-less conditions. The transformation has been accomplished by employing NH2OH⦁HCl as a reagent and amines as substrates. The developed method is achieved in the absence of metals and hazardous reagents. A series of amines were explored to obtain the N-formylation and N-acylation reactions with excellent yields (81-96%) of products. The DFT analysis was also performed, which provides a clear understanding of the described N-formylation process. The postulated mechanism is well supported by the control experiments. [ABSTRACT FROM AUTHOR]

This document provides a detailed description of the synthesis and characterization of various compounds, specifically pyrimidine-fused benzothiazoles. The compounds are synthesized using a Pd-catalyzed annulation reaction and are characterized using spectroscopic techniques such as NMR and ESI-HRMS. The yields, physical properties, and spectral data of each compound are provided. The document also includes supporting information and a graph, and the authors of the document are listed at the end. This information can be valuable for researchers studying the synthesis and properties of these compounds. [Extracted from the article]

This article discusses the challenges and importance of selectively functionalizing C-H bonds in organic molecules, particularly C(sp3)-H bonds. The authors focus on the azolation of benzylic C-H bonds under photoredox catalysis and aim to understand the reaction mechanism and regioselectivity. Through a computational study using density functional theory, they investigate the full photoredox catalytic cycle and characterize the steps involved in the reaction. The study provides insights into the origins of regioselectivity and contributes to the understanding of C-H azolation within photoredox systems. [Extracted from the article]

A rise in infections caused by methicillin- and vancomycin-resistant Staphylococcus aureus is an increasing global health concern that causes boosting illness and death. The growing problem of drug resistance has emphasized the need to discover and develop new antibacterial agents that work through different mechanisms. To address this issue and create prospective antibacterial drugs, numerous chalcone derivatives of thiazolidine-2,4-dione have been designed, synthesized, and evaluated against three bacterial strains and one fungal strain. Compounds 7a, 7h, and 7k were found to selectively inhibit S. aureus at a concentration of 25 μg/mL but were inactive toward gram-negative bacteria. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: We describe an iron‐catalyzed amide bond formation from readily available carboxylic acids and isocyanates. This method utilizes an abundant and biocompatible iron catalyst and easily accessible starting materials, generates CO2 as the only byproduct, and features broad substrate scopes with good functional group compatibility. Therefore, it provides a cost‐effective and practical protocol to access a diverse variety of amides. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: We describe an iron‐catalyzed amide bond formation from readily available carboxylic acids and isocyanates. This method utilizes an abundant and biocompatible iron catalyst and easily accessible starting materials, generates CO2 as the only byproduct, and features broad substrate scopes with good functional group compatibility. Therefore, it provides a cost‐effective and practical protocol to access a diverse variety of amides. [ABSTRACT FROM AUTHOR]

Copper sulfate catalyzed an efficient, inexpensive, and environment-friendly protocol that has been developed for N-arylation of amines with 1,3-cyclohexadione-derived aryliodonium ylides in water as a green solvent. Aromatic primary amines substituted with electron-donating as well as electron-withdrawing groups on the aryl ring reacted smoothly with iodonium ylides to give the corresponding diarylamines with good to excellent yields. Also, secondary amines underwent N-arylation to deliver tertiary amines with moderate yields.

Atom-economical, eco-efficient, metal- and chemical oxidant-free formation of C–C and C–N bond from C(sp2)−H and C(sp3)−H of arenes toward the direct synthesis of biaryls and anilides or N-benzylamides under mild electro-oxidative conditions is described. The products of C–C and C–N coupling are obtained in up to 88% yields. Aromatic substrates that are oxidized at potentials less positive than +2 V or have bulky bromine or iodine substituents undergo homo-coupling reactions by anodic oxidation to form biaryls or dimers. Aromatic substrates that are difficult to oxidize (Eox > +2 V) preferentially form anilides and N-benzylamides upon anodic oxidation. The presence of a chlorine substituent on the aromatic ring leads to the formation of both biaryls and anilides during electro-oxidation.

A facile and effectual regioselective one‐pot synthesis protocol has been developed for the construction of pyrido[1,2‐a]benzimidazole and its derivatives using Copper(I) bromide as the catalyst, 1,10‐phenanthroline as ligand, and K3PO4 (Tripotassium phosphate) as the base in Dimethyl sulfoxide as solvent at 110 °C for 12 h. The reaction conditions were optimized by screening various copper catalysts, ligands, solvents, and bases. The substrate scope of the reaction was also carried out with electron‐withdrawing and donating functional groups to prepare novel functionalized regioselective benzimidazole compounds in good to excellent yields. All the isolated compounds were characterized by 1H, 13C, and 19F NMR. [ABSTRACT FROM AUTHOR]

A low temperature hydrogen borrowing approach to generate secondary amines using benzimidazole-based N-heterocyclic carbene (BNHC) ruthenium complexes is reported. A series of the piano-stool complexes of the type [(η6-p-cymene)(BNHC)RuCl2] (1a-g) were synthesized via one-pot reaction of the NHC salt precursor, Ag2O, and [RuCl2(p-cymene)]2 and characterized using conventional spectroscopic techniques. The geometry of two precursors, [(η6-p-cymene)(Me4BnMe2BNHCCH2OxMe)RuCl2] (1f) and [(η6-pcymene)(Me5BnMe2BNHCCH2OxMe)RuCl2] (1g), was studied by single crystal X-ray diffraction. These catalysts were found to dehydrogenate alcohols efficiently at temperatures as low as 50 °C to allow Schiff-base condensation and subsequent imine hydrogenation to afford secondary amines. Notably, this ruthenium-based procedure enables the N-alkylation of aromatic and heteroaromatic primary amines with a wide range of primary alcohols in excellent yields of up to 98%. The present methodology is green and water is liberated as the sole byproduct. [ABSTRACT FROM AUTHOR]

The functionalization of C-H bonds in light alkanes, particularly to form C-N bonds, remains a challenge. We report the dehydrogenative coupling of amides with C1-C4 hydrocarbons to form N-alkyl amide products with tBuOOtBu as oxidant, and a copper complex of a phenanthroline-type ligand as catalyst. The reactions occurred in good yields in benzene or supercritical carbon dioxide as solvents. This strategy allowed for the determination of the relative reactivity of these alkane C-H bonds toward this amination process and showed, in contrast to prior work with larger alkanes, that the reactivity correlated with bond dissociation energies.

C-N bond formation, C-C coupling, palladium catalysis, cascade reaction, 2,6-disubstituted pyrazines Likewise, dehydrogenative dimerization of 1,2-diols with NH SB 3 sb in the presence of Ru catalyst [15] gives rise to symmetrical 2,6-disubstituted pyrazines, albeit accompanied by a mixture of unsymmetrical 2,5-disubstituted pyrazines (Scheme 1 A). Keywords: C-C coupling; C-N bond formation; palladium catalysis; cascade reaction; 2,6-disubstituted pyrazines EN C-C coupling C-N bond formation palladium catalysis cascade reaction 2,6-disubstituted pyrazines 2554 2560 7 07/31/23 20230817 NES 230817 Graph Pyrazines are important N-heterocycles and occur ubiquitously in a wide variety of natural products, [1][2] bioactive agents, [3] agrochemicals, [4] and dyes. [Extracted from the article]

Nitrogen-containing heterocycles such as morpholin-2-ones are structural elements of many biologically active substances, as well as useful synthetic intermediates. To be able to functionalize them regioselectively in an easy, atom-efficient, and environmentally friendly manner is highly desirable. A procedure for cross-dehydrogenative coupling between morpholinones and cyclic imides was developed addressing these requirements. An earth-abundant metal catalyst, copper(I) chloride, in the presence of acetic acid, and with molecular oxygen as the sole oxidant, operating under mild conditions, afforded the desired C–N coupled products in high yields. Besides being potentially biologically active, as many members of both families of compounds are, the products themselves may be suitable substrates for functionalized polymers, e.g., poly(β-aminoesters) or even for PROTACs. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: The visible light‐driven C2 or C3 amination of indoles without any additives was initiated via electron donor‐acceptor (EDA) complex formed by indole and N‐aminopyridinium salt. This method was compatible with a wide range of substrates and could proceed smoothly without the addition of any photocatalysts, transition‐metal catalysts, or bases. A variety of studies were carried out to examine the presence of EDA complex. [ABSTRACT FROM AUTHOR]

Dioxazolones, which are potent amide precursors, have been widely explored for the formation of C–N bonds with the help of transition-metal catalysts. Here, we highlight our recent studies on the synthesis of N -aryl amides using dioxazolones and boronic acids in the presence of copper(I) chloride under mild conditions. The versatility of the developed reaction is demonstrated by its wide range of functional-group tolerances as well as the release of nontoxic carbon dioxide. Optimization screenings reveal that a fluorine additive improves the desired reactivity toward the intended transformation. The addition of triphenylphosphine results in an N -acyl iminophosphorane, suggesting the involvement of an N -acyl nitrene intermediate in this transformation. [ABSTRACT FROM AUTHOR]

Amide functional groups are a structural feature in a vast array of beneficial organic molecules. This has resulted in a surge in new methodologies developed to enable access to this functional group using a broad range of coupling partners. Herein, we report a palladium-catalysed reductive aminocarbonylation of aryl bromides and iodides with nitroarenes to afford the respective amide products. The developed protocol employs Mo(CO)6 as a carbonyl source and a combination of Zn and TMSCl as co-reducing agents. For most substrates, the anticipated amide products were obtained in modest to high amide product yields.

A straightforward and convenient synthesis of symmetrical and unsymmetrical thiourea derivatives by the reaction of primary amines and carbon disulfide in the presence of a Zn catalyst is presented. Under modest reaction conditions, a range of biologically relevant thiourea derivatives can be produced in good to outstanding yields without a lengthy work-up. A variety of primary aliphatic and aromatic amines with various substituted functional groups were transformed into thiourea derivatives. Zn-mediated symmetric thiourea creation occurs at room temperature for aliphatic amines, whereas for aromatic amines it occurs at 60°C. However, unsymmetrical thiourea for aliphatic amines occurs at 0°C. Benefits of this method include environment-friendly reaction conditions, sustainability, and enumerating tolerance of functional groups such as hydroxyl and halides. Experimental observations were rationalized by DFT calculations based on transition structures and zwitterionic intermediate stabilities. [ABSTRACT FROM AUTHOR]

A plenty of cytochrome P450s have been annotated in the Daldinia eschosholzii genome. Inspired by the fact that some P450s have been reported to catalyze the carbon-nitrogen (C–N) bond formation, we were curious about whether hybrids through C–N bond formation could be generated in the indole-3-carbinol (I3C) exposed culture of D. eschscholzii. As expected, two skeletally undescribed polyketide-indole hybrids, designated as indolpolyketone A and B (1 and 2), were isolated and assigned to be constructed through C–N bond formation. Their structures were elucidated by 1D and 2D NMR spectra. The absolute configurations of 1 and 2 were determined by comparing the recorded and calculated electronic circular dichroism (ECD) spectra. Furthermore, the plausible biosynthetic pathways for 1 and 2 were proposed. Compounds 1 and 2 exhibited significant antiviral activity against H1N1 with IC50 values of 45.2 and 31.4 μM, respectively. In brief, compounds 1 and 2 were reported here for the first time and were the first example of polyketide-indole hybrids pieced together through C–N bond formation in the I3C-exposed culture of D. eschscholzii. Therefore, this study expands the knowledge about the chemical production of D. eschscholzii through precursor-directed biosynthesis (PDB).

An unusual iridium dimer 1, [(4-cpbo)Ir(μ-Cl)(μ-O)Ir(4-cpbo)] (4-cpbo = 4-chlorophenylbenzoxazolato-N,C2), was obtained by the oxidative addition of oxygen and reductive elimination of chlorine from a precursor [(4-cpbo)2Ir(μ-Cl)]2. This iridium dimer 1 has a metastable structure with an asymmetric bridge, can spontaneously release metalloradicals and coordinatively unsaturated species in solution at room temperature, and exhibits high catalytic ability for synthetic applications. [ABSTRACT FROM AUTHOR]

An aryl iodide catalyzed intramolecular oxidative transformation of diphenylpropanamide derivatives is described that can readily afford the C–N/C–O coupling products in a single step. The speed of the 1,3-aryl iodide migration process determines the diversity of target compound generation in this reaction. This straightforward approach can be performed with the use of inexpensive and readily available catalyst, transition-metal-free, mild conditions and good functional group tolerance.

We report an efficient and selective methodology for the direct cross-coupling of alcohols with N-nucleophiles mediated by N-iodosuccinimide (NIS) as the non-metal, commercially available, low-cost, and most effective precatalyst among the N-halosuccinimides (NXSs) under mild reaction conditions enhancing the green chemical profiles of these reactions. The scale-up procedure was accomplished with almost quantitative yield, verifying the presented method's synthetic applicability and potential for industrial application. [ABSTRACT FROM AUTHOR]

Straightforward synthesis of quinazolinones having N-fused medium-sized ring urea was accomplished. Key intermediates were tert -butyl {2-[4-oxo-2-(4-oxopentyl)quinazolin-3(4 H)-yl]ethyl}carbamates derived from copper-catalyzed domino reaction of tert -butyl [2-(2-iodobenzamido)ethyl]carbamates and cyclic enaminones. Steric hindrance of cyclic enaminones played an important role in the formation of quinazolinone ring. The eleven-membered ring urea moiety was readily achieved by direct cyclization using 1,1′-carbonyldiimidazole (CDI) of diamino intermediate generated by readily reductive amination and deprotection of tert -butyl {2-[4-oxo-2-(4-oxopentyl)quinazolin-3(4 H)-yl]ethyl}carbamates. [ABSTRACT FROM AUTHOR]

Nitrogen-containing heterocycles such as morpholin-2-ones are structural elements of many biologically active substances, as well as useful synthetic intermediates. To be able to functionalize them regioselectively in an easy, atom-efficient, and environmentally friendly manner is highly desirable. A procedure for cross-dehydrogenative coupling between morpholinones and cyclic imides was developed addressing these requirements. An earth-abundant metal catalyst, copper(I) chloride, in the presence of acetic acid, and with molecular oxygen as the sole oxidant, operating under mild conditions, afforded the desired C–N coupled products in high yields. Besides being potentially biologically active, as many members of both families of compounds are, the products themselves may be suitable substrates for functionalized polymers, e.g., poly(β-aminoesters) or even for PROTACs.

An iridium-catalyzed reaction protocol has been developed to achieve the oxidative C–H/N–H annulation of benzamides with cyclopropanols as C1 synthon. Structurally diverse isoindolin-1-ones were furnished via sequential C–H/C–C cleavage and C–C/C–N bond formation. [ABSTRACT FROM AUTHOR]

[Display omitted] • Iron catalysis for C N bond formation. • Iron-porphyrin catalysis. • Iron catalysis for C(sp2)–H & C(sp3)–H activation & C N bond formation. • Iron catalysis for high-valued N -heterocycles/molecules. • Metalloradical catalysis by iron-porphyrin catalysis. • Denitrogenative transformation of tetrazoles by iron catalysis. Direct C N bond forming reaction by utilizing the non-precious transition metals is an attractive field of research in organic synthesis. Unlike the conventional use of precious metals like rhodium, palladium, ruthenium, and iridium that are commonly used in these reactions, the use of non-precious metals, particularly those are non-toxic and high abundant, holds distinct attention owing to the increasing demand of sustainable chemical processes. Among them, iron catalysis offers notable advantages for sustainable chemical synthesis. Iron-catalysed nitrene transfer reactions have emerged as robust and eco-friendly methods for constructing various valuable C N bonds. In this review, we provide a comprehensive overview of the advancements in iron catalysis for the nitrene transfer reactions aimed at synthesizing diverse C N bonds. [ABSTRACT FROM AUTHOR]

C-N bond formation is one of the most commonly used reactions in medicinal chemistry. Herein, we report an efficient Pd-promoted hydroamination reaction between DNA-conjugated aryl alkenes and a wide scope of aliphatic amines. The described reactions are demonstrated in good to excellent conversions to furnish C (sp3)–N bonds on DNA. This DNA-compatible transformation has strong potentials for the application into DNA-encoded library synthesis.

As the nitrogen‐containing compounds have broad scope in biological, pharmaceutical, drug delivery, and material science, the C–N bond formation has vital role in synthetic chemistry. To provide a path for the inclusion of nitrogen in organic molecules, a facile establishment of C–N bonds is crucial. Manganese being inexpensive, nontoxic, and earth abundant is found to be a perfect catalyst to carry out amination, instead of using harsh reaction conditions or toxic metal catalysts. Herein, we discuss the manganese‐catalyzed amination reactions focusing on various manganese based catalysts for the C–N bond formation and covers the literature until 2020. [ABSTRACT FROM AUTHOR]

An unusual iridium dimer 1, [(4-cpbo)Ir(μ-Cl)(μ-O)Ir(4-cpbo)] (4-cpbo = 4-chlorophenylbenzoxazolato-N,C2), was obtained by the oxidative addition of oxygen and reductive elimination of chlorine from a precursor [(4-cpbo)2Ir(μ-Cl)]2. This iridium dimer 1 has a metastable structure with an asymmetric bridge, can spontaneously release metalloradicals and coordinatively unsaturated species in solution at room temperature, and exhibits high catalytic ability for synthetic applications.

A one-pot direct synthesis of xanthine and uric acid derivates is reported. This simple yet efficient methodology illustrates concurrent formation of two C–N bonds using CuBr2 as catalyst and one of those C–N bonds is formed by uracil C6–H bond activation. [ABSTRACT FROM AUTHOR]

Several catalytic reactions such as Ullmann, Chan–Lam, Huisgen 1,3‐dipolar cycloaddition, [2 + 3] cycloaddition, condensation, and coupling reactions under suitable conditions have been used for the synthesis of fundamental structures containing a carbon–nitrogen (C–N) bond. Graphene oxide (GO) and its derivatives as heterogeneous catalysts have attracted considerable attention for the synthesis of organic building blocks. Loading of GO derivatives with copper complexes or nanoparticles, as one of the most abundant and low toxic transition metals, allowed to design new composites with predominant ability to C–N bond formation. In this review article, we present a comprehensive overview on the synthesis of building blocks containing a C–N bond such as amines, triazoles, tetrazoles, propargyl amines, imidazoles, and benzodiazepines using GO derivatives loaded with copper complexes or nanoparticles. [ABSTRACT FROM AUTHOR]

We report an efficient and selective methodology for the direct cross-coupling of alcohols with N-nucleophiles mediated by N-iodosuccinimide (NIS) as the non-metal, commercially available, low-cost, and most effective precatalyst among the N-halosuccinimides (NXSs) under mild reaction conditions enhancing the green chemical profiles of these reactions. The scale-up procedure was accomplished with almost quantitative yield, verifying the presented method’s synthetic applicability and potential for industrial application.

A copper-catalyzed tandem reaction has been developed for the synthesis of 1,2,3-triazole-fused indole derivatives. This protocol allowed us to access a wide range of 1,2,3-triazole-fused indole derivatives in moderate to excellent yields. The 1,2,3-triazole-fused indole derivatives emit blue and greenish light when excited at 365 nm. The products were further explored for their quantum efficiency and photophysical properties. [ABSTRACT FROM AUTHOR]

Benzimidazole is an important heterocycle that is widely researched and utilized by the pharmaceutical industry and is one of the five most commonly used five-membered aromatic heterocyclic compounds approved by the US Food and Drug Administration. In view of their wide-ranging bioactivities, systems containing benzimidazole as one of the moieties occupy a special place among other benzimidazole derivatives. Since 2010, many improved synthetic strategies have been developed for the construction of hetaryl- and arylbenzimidazole molecular scaffolds under environmentally benign conditions. This review emphasizes the recent trends and modifications frequently used in the synthesis of derivatives of benzimidazole such as the Phillips–Ladenburg and Weidenhagen reactions, as well as entirely new methods of synthesis, involving oxidative cyclization, cross-coupling, ring distortion strategy, and rearrangements carried out under environmentally benign conditions. 1 Introduction 2 From 1,2-Diaminobenzenes with Various One-Carbon Unit Suppliers 2.1 Phillips–Ladenburg Reaction 2.1.1 With (Het)arenecarboxylic Acids 2.2.2 With (Het)arenecarboxylic Acid Derivatives 2.2 Weidenhagen Reaction 2.2.1 With (Het)arenecarbaldehydes or (Het)aryl Methyl Ketones 2.2.2 With Primary Alcohols 2.2.3 With Primary Alkylamines 2.2.4 With 2-Methylazaarenes 2.2.5 With Other One-Carbon Fragment Suppliers 3 From 2-Haloacetanilides and Amines 4 From Amidines 5 From Tetrahydroquinazolines 6 Mamedov Rearrangement 7 Conclusions and Outlook [ABSTRACT FROM AUTHOR]

[Display omitted] We report, regio and stereoselective addition of N -heterocycles on internal alkynes through C(sp2)-N(sp3) bond formation. We have synthesized a series of 1H -indole, 1H- benzimidazole and tetrahydroquinolines (THQ) functionalized Maleate, Fumarate and Acrylate derivatives through N - alkenylation reactions. We have demonstrated the selective formation of E- Isomers. Further substrate dependent formation of E and Z isomers are also observed. [ABSTRACT FROM AUTHOR]

[Display omitted] Molecules containing C–N bonds are of paramount importance in a diverse array of organic-based materials, natural products, pharmaceutical compounds, and agricultural chemicals. Biocatalytic C–N bond-forming reactions represent powerful strategies for producing these valuable targets, and their significance in the field of synthetic chemistry has steadily increased over the past decade. In this review, we provide a concise overview of recent advancements in the development of C–N bond-forming enzymes, with a particular emphasis on the inherent chemistry involved in these enzymatic processes. Overall, these enzymatic systems have proven their potential in addressing long-standing challenges in traditional small-molecule catalysis. [ABSTRACT FROM AUTHOR]

The synthesis of N‐substituted amines is one of the key transformations in synthetic chemistry and chemical industry, because amines are ubiquitous in the syntheses of agrochemicals, pharmaceuticals, flavorings, fragrances, and advanced materials. In order to realize the clean and economic synthesis of N‐substituted amines, several aspects should be concerned. 1) The application of alkyl halides as alkylation reagents should be replaced by alcohol and alkane; 2) the employment of amines as nitrogen sources can be replaced by nitrobenzene, nitrile and ammonia; 3) the application of environmentally benign and low‐cost starting materials, such as CO2, HCHO, biomass resources, for the nitrogen‐containing chemicals synthesis should be established; and 4) economic, green and efficient catalyst should be developed for the above transformations. In this account, we describe our results in the clean and economic synthesis of N‐substituted amines with amine, ammonia, nitrobenzene or nitrile as nitrogen sources and alcohol, alkane or CO2, HCHO, CO, and biomass resources as alkylation or carbonylation reagents. What is the most favorite and original chemistry developed in your research group? Efficient and economic heterogeneous catalyst for catalytic amination. How do you get into this specific field? Could you please share some experiences with our readers? I got my introduction to fine chemical synthesis with heterogeneous catalyst during the post‐graduate and post‐doctor periods. Till now, the clean and economic synthesis of some fine chemicals still remains a big problem in China. Therefore, our group has been concentrating on catalyst design and preparation for amination since 11 years ago. Typically, we want to explore some novel catalyst systems to bridge the heterogeneous and homogeneous catalysis. What is the most important personality for scientific research? I think the originality and creativity are very important for the scientific research. What are your hobbies? What's your favorite book(s)? Reading and walking. I like to read history books. How do you keep balance between research and family? Although it is difficult, I try to keep a balance between research and family. Who influences you mostly in your life? My Ph.D. supervisor, Prof. Youquan Deng, and postdoctoral collaborating advisor, Prof. Matthias Beller. [ABSTRACT FROM AUTHOR]

For years, metal–nitrene-transfer reactions have been mainly directed toward C=C bond aziridination or C–H bond amidation reactions. In the last decade, multiple efforts have been made to develop new synthetic approaches to expand the applicability of this powerful tool, resulting in the synthesis of complex structures from relatively simple starting materials. Here, we present our contributions to the area with several novel and, to some degree, unexpected transformations developed by our research group. The catalysts for these nitrene-transfer reactions are copper or silver complexes bearing hydrotrispyrazolyl (scorpionate) ligands. These transformations have contributed to an expansion of the scope of organic compounds accessible by nitrene-transfer reactions and to an understanding of the reactivity of metallonitrene species toward the oxidation of less-explored organic substrates. 1 Introduction 2 Synthesis of 1,2-Dihydropyridines from Furans 3 Regio- and Stereoselective Aziridination of Dienes 4 Chemoselective Synthesis of Aminimides from Amines 5 Synthesis of Sulfinamides and Isothiazoles from Alkynes 6 Formation of Azetidines and Methylene Aziridines from Allenes 7 Conclusion [ABSTRACT FROM AUTHOR]

Copper-mediated carbon–heteroatom bond-forming reactions involving a wide range of substrates have been in the spotlight for many organic chemists. This review highlights developments between 2010 and 2019 in both stoichiometric and catalytic copper-mediated reactions, and also examples of nickel-mediated reactions, under modified Chan–Lam cross-coupling conditions using various nucleophiles; examples include chemo- and regioselective N-arylations or O-arylations. The utilization of various nucleophiles as coupling partners together with reaction optimization (including the choice of copper source, ligands, base, and other additives), limitations, scope, and mechanisms are examined; these have benefitted the development of efficient and milder methods. The synthesis of medicinally valuable or pharmaceutically important nitrogen heterocycles, including isotope-labeled compounds, is also included. Chan–Lam coupling reaction can now form twelve different C–element bonds, making it one of the most diverse and mild reactions known in organic chemistry. 1 Introduction 2 Construction of C–N and C–O Bonds 2.1 C–N Bond Formation 2.1.1 Original Discovery via Stoichiometric Copper-Mediated C–N Bond Formation 2.1.2 Copper-Catalyzed C–N Bond Formation 2.1.3 Coupling with Azides, Sulfoximines, and Sulfonediimines as Nitrogen- Nucleophiles 2.1.4 Coupling with N , N -Dialkylhydroxylamines 2.1.5 Enolate Coupling with sp3-Carbon Nucleophiles 2.1.6 Nickel-Catalyzed Chan–Lam Coupling 2.1.7 Coupling with Amino Acids 2.1.8 Coupling with Alkylboron Reagents 2.1.9 Coupling with Electron-Deficient Heteroarylamines 2.1.10 Selective C–N Bond Formation for the Synthesis of Heterocycle-Containing Compounds 2.1.11 Using Sulfonato-imino Copper(II) Complexes 2.2 C–O Bond Formation 2.2.1 Coupling with (Hetero)arylboron Reagents 2.2.2 Coupling with Alkyl- and Alkenylboron Reagents 3 C–Element (Element = S, P, C, F, Cl, Br, I, Se, Te, At) Bond Forma tion under Modified Chan–Lam Conditions 4 Conclusions [ABSTRACT FROM AUTHOR]

We report the synthesis of a vanadium(V) complex characterized by FT-IR and 1H NMR spectroscopy. The structure of the complex was established by single crystal X-ray crystallography. We also carried out the catalytic oxidation of benzyl alcohol, hetero-aryl alcohols and propargylic alcohols. Tandem synthesis of oximes from alcohols were also carried out using our vanadium(V) complex. The newly synthesized complex acts as a catalyst for oxidation reactions and tandem synthesis of oxime from alcohols. [ABSTRACT FROM AUTHOR]

An efficient Pd2(dba)3-catalyzed amination of C5-bromo-imidazo[2,1-b][1,3,4]thiadiazole using conventional heating is reported. The C5-bromoimidazo[2,1-b][1,3,4]thiadiazole was synthesized using a multistep approach which started by cyclization of thiosemicarbazide with a carboxylic acid to give 2-amino[1,3,4]thiadiazoles which were further treated with 2-haloketones to give imidazo[2,1-b][1,3,4]thiadiazoles. Then, the bromination of imidazothiadiazole was done using N-bromosuccinimide to give the C5-bromo-imidazo[2,1-b][1,3,4]thiadiazole. Afterward, various C-N bond-forming approaches were attempted such as SNAr, Cu(I), Cu(II), Pd(OAc)2, Pd2(dba)3 catalyst with different ligand, additive, base, solvent and temperature conditions. Out of various approaches used, only Buchwald Hartwig amination, performed with conventional heating, gave N-arylamine-5-imidazothiadiazoles. Then, 10 different anilines with different electron-withdrawing and donating groups at different positions were employed to examine the scope and limitations of the method. Salient features of this method include conventional heating in a Schlenk tube as the reaction condition, the absence of the use of toxic isocyanides, the wide nature of substituent tolerance with anilines, and moderately good product yields. [ABSTRACT FROM AUTHOR]