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This document provides information on the synthesis and characterization of various compounds, including β-aminonitriles, β-amino sulfones, and dimethyl aspartates. The compounds were synthesized using lanthanoid triflates Yb(OTf)3 and Tb(OTf)3 as catalysts and the reactions were optimized for yield. The document also includes spectroscopic data, such as melting points and NMR spectra, for the compounds. The data presented in the document match those previously reported in the literature. The document acknowledges the facilities used for the research and dedicates the work to the late Prof. Ibrahim Ibnusaud. [Extracted from the article]

This article explores the challenges and strategies involved in selectively adding carbon-based units to nonactivated alkenes. The authors focus on the use of directing groups, specifically a quinolinamide directing group, in a nickel-catalyzed reaction. This method allows for the efficient synthesis of branched molecules and demonstrates a high level of selectivity. The authors provide experimental results and optimization of reaction conditions to support their findings. Additionally, the article discusses the broad functional-group tolerance of the reaction and its potential applications in pharmaceutical modifications and large-scale reactions. [Extracted from the article]

This article discusses the use of aromatic amine catalysts in a specific chemical reaction. The researchers conducted experiments using different catalysts and found that aryl amines were more effective than alkyl amines. They also discovered that a commercially available proton sponge showed promise as a catalyst. The article explores the catalytic activity of a specific catalyst called cat14 and compares it to other catalysts. While cat14 showed promising results, the study concludes that another scaffold called phenotellurazine performed better in the reactions. Further research is being done to improve the phenotellurazine scaffold and other catalysts. [Extracted from the article]

This article discusses recent developments in the photocatalytic reduction of nitro compounds to valuable intermediates, such as amines and azo compounds. Nitro compounds are widely used in various industries but pose environmental and health hazards due to their toxicity and nondegradability. Traditional reduction methods often use harsh conditions and toxic chemicals, making the utilization of photocatalytic organic transformations an attractive option for sustainable and green chemical processes. The article provides an overview of different photocatalytic systems, including metal-organic frameworks, semiconductors, and nanocomposites, and explores their synthesis, performance, stability, recyclability, and selectivity. The use of hole scavengers and sacrificial reagents to enhance the reduction process is also mentioned. The studies demonstrate the potential of these photocatalytic systems for efficient and environmentally friendly nitro compound reduction. [Extracted from the article]

Moreover, 2-aminobenzoic acids having electron-delocalization substituents, such as phenyl, acetyl, carbamate, and urea gave no yield of the corresponding products (entries 5-7). [35][36][37] We found that the nucleophilicity of nitrogen of 2-(benzylamino)benzoic acids was crucial to result in good yields of products from 2-(benzylamino)benzoic acids bearing electron-donating substituents on benzene ring. Keywords: quinazolinediones; cylic ureas; organocatalysis; intramolecular C-N amide bond formation; Tiemann rearrangement EN quinazolinediones cylic ureas organocatalysis intramolecular C-N amide bond formation Tiemann rearrangement 2052 2058 7 10/09/23 20231024 NES 231024 Graph Quinazolinediones are one of the most important nitrogen-containing heterocyclic compounds due to their common occurrence in natural products. Another key factor of the reaction was the electrophilicity of -chloroaldoxime I O i -methanesulfonates resulting in good yields with electron-withdrawing substituents and moderate yields from aliphatic -chloroaldoxime I O i -methanesulfonates. [Extracted from the article]

However, for this endeavor we would directly use aniline B 22 b [21] to conclude our MCR procedure, because necessity required it; condensation of aniline B 22 b with either propionaldehyde or isobutyraldehyde had failed to afford a sufficiently pure imine to proceed. Keywords: ortho -quinone methides; marilines; imines; dihydrooxazoles; anilines; isoindolin-1-ones; phthalimidines; salicylaldehydes EN ortho -quinone methides marilines imines dihydrooxazoles anilines isoindolin-1-ones phthalimidines salicylaldehydes 3297 3302 6 09/29/23 20231018 NES 231018 Graph Numerous phthalimidines found in nature display a wide range of biological activities. The solution was quenched with saturated NaHCO SB 3 sb solution (3 mL) and extracted with Et SB 2 sb O (3 × 3 mL). Specifically, we have shown that various I o i -QM intermediates can be engaged by anilines, dihydrooxazoles, and imines to arrive at N-arylated, N-hydroxy ethylated, and free-N amines, respectively. [Extracted from the article]

Notably, instead of using ( I E i )-3-bromoprop-1-ene-1-sulfonyl fluoride ( B 2a b ), the use of ( I E i )-3-chloroprop-1-ene-1-sulfonyl fluoride ( B 2b b ) for the nucleophilic substitution reaction with aniline ( B 1a b ) was also examined. [60] Herein, we report an efficient protocol for constructing , -unsaturated -amino sulfonyl fluorides via chemo- and stereoselective nucleophilic substitution reactions of ( I E i )-3-bromoprop-1-ene-1-sulfonyl fluoride with aromatic amines in the presence of a base (Scheme 2). Keywords: , -unsaturated -amino sulfonyl fluorides; allylic amines; vinyl sulfonyl fluorides; click chemistry; covalent inhibitors EN , -unsaturated -amino sulfonyl fluorides allylic amines vinyl sulfonyl fluorides click chemistry covalent inhibitors 3373 3381 9 09/29/23 20231018 NES 231018 Graph As highly important building blocks for various bioactive compounds, allylamines are found widely in natural products and pharmaceutical molecules [1] such as colchicine, [8] dehydroabietylamine, [9] and terbinafine [4] (Figure 1a). [59] (2) The primary amine firstly undergoes a nucleophilic substitution reaction with ( I E i )-3-bromopropen-1-ene-1-sulfonyl fluoride to produce the desired product which then transforms into a sulfonyl amide via a SuFEx reaction. [Extracted from the article]

Keywords: heterogeneous catalyst; 3-aminoalkylated indoles; solvent-free protocol; microwave-assisted; multicomponent reaction; one-pot synthesis EN heterogeneous catalyst 3-aminoalkylated indoles solvent-free protocol microwave-assisted multicomponent reaction one-pot synthesis 3153 3158 6 09/11/23 20231004 NES 231004 Graph Multicomponent reactions (MCRs), [1] primarily focusing on concepts such as atom economy and green chemistry have achieved considerable attention of scientific community globally. To the best of our knowledge no report has been published for the synthesis of 3-alkylaminoalkylated indoles with primary amines under microwave irradiation treated over heterogeneous catalyst in one-pot three-component reaction conditions. Heterogeneous catalyst, 3-aminoalkylated indoles, solvent-free protocol, microwave-assisted, multicomponent reaction, one-pot synthesis. [Extracted from the article]

It should be mentioned that so far electrocarboxylation has been mainly explored for the carboxylation of olefins and imines, and only a few reports have been published on direct electrocatalytic C(sp SP 3 sp )-H bond carboxylation reactions. In previous studies, transition-metal or transition-metal-free methodologies proceeded through C(sp SP 3 sp )-H bond carboxylation reactions via enolate chemistry to trap a CO SB 2 sb molecule in order to give carboxylation products. Recent Advances on the Carboxylations of C(sp3)-H Bonds Using CO2 as the Carbon Source Keywords: carbon dioxide; transition-metal; transition-metal-free; thermochemical strategy; visible-light-induced photocatalysis; electrocatalysis; reductive C-H carboxylations; carboxylic acids EN carbon dioxide transition-metal transition-metal-free thermochemical strategy visible-light-induced photocatalysis electrocatalysis reductive C-H carboxylations carboxylic acids 1327 1342 16 07/11/23 20230725 NES 230725 Graph 1 Introduction The carboxylic acid unit is omnipresent in bioactive drug molecules, pharmaceuticals, natural products, and agrochemicals. [Extracted from the article]

A facile reductive amination procedure for electron-poor heterocyclic amines with aromatic and aliphatic aldehydes has been developed. The key to success was the use of triethylsilane (Et3 SiH) as reducing agent, in combination with trifluoroacetic acid (TFA) in refluxing CH2 Cl2. The reductive aminations are fast and clean, and allow for the isolation of the alkylated amines in high yields and purity after crystallization or chromatographic purification. The robustness and scalability of the process has been demonstrated for one substrate combination on 750 g scale, leading to the isolation of the corresponding product in 93% yield. [ABSTRACT FROM AUTHOR]

New methods for the synthesis of 1,3-diaryltriazenes and azo dyes from aryl amines are reported. Both methods involve the formation of aryl diazonium intermediates via the transnitrosation of aryl amines with N -nitrososulfonamides. Each two-step transformation may be performed in one reaction vessel at room temperature with no precautions taken to exclude air or moisture. Several triazene and azo dye structures are reported here for the first time, demonstrating the utility of operating the two-step reaction sequence under mild conditions. [ABSTRACT FROM AUTHOR]

An account of our development of reactions to construct N -heterocycles by triggering cyclization–migration tandem reactions from aryl azides, nitroarenes, and aryl amines is described. The reactivity patterns of metal N -aryl nitrenes, nitrosoarenes, N -aryl nitrogen radical anions, and N -aryl nitrenoids are compared. 1 Introduction 2 Unlocking the Reactivity Embedded in Aryl Azides 3 Exploiting the Reactivity of Nitrosoarenes Generated from Nitroarenes 4 Radical Anion N -Aryl Nitrogen Reactive Intermediates from Nitroarenes 5 Oxidation of Aryl Amines to Access Electrophilic N -Aryl Nitrenoids 6 Conclusion [ABSTRACT FROM AUTHOR]

Nitrogen-containing polyaromatic compounds have been prepared in one step by combining diols and anthracenyl or naphthyl amines via acceptorless dehydrogenative condensation with ZnO and Pt/Al2 O3 as heterogeneous catalysts. [ABSTRACT FROM AUTHOR]

An efficient protocol for the amidation of hydrazide with amine has been developed by utilizing I2 as an oxidant under metal- and base-free conditions at room temperature. N-Acylation products of amines were obtained in good to excellent yields without using toxic reagents. This method is operationally straightforward and tolerates aliphatic/aromatic and primary/secondary amines with different hydrazides. [ABSTRACT FROM AUTHOR]

Herein, we describe the synthesis of a wide variety of imines through oxidative coupling of alcohols and aromatic amines catalyzed by Mn complexes bearing N^N triazole ligands. A wide variety of imines in excellent yields (up to 99%) have been prepared. Mn-based catalysts proved to be highly efficient and versatile, allowing for the first time the preparation of several imines containing N-based heterocycles. [ABSTRACT FROM AUTHOR]

A bimetallic catalytic combination of Mn(OAc)2 and Cu(OAc)2 was found to be significantly effective for the Buchwald-type C–N cross-coupling of aryl chlorides and amines. The reaction was markedly affected by the presence of a poly(amidoamine) dendrimer as a promoter that also possesses the advantages of being stable, nontoxic, biocompatible, nonimmunogenic, and acting as a soluble support for the transition-metal complex. Although, manganese is cheap and environmentally benign, it has not been fully exploited, due to its low intrinsic catalytic activity. Here, the catalytic potential of manganese was drastically increased by the presence of another metal salt, Cu(OAc)2. In the bimetallic composition, Mn significantly influenced the activity and selectivity, and played a vital role in catalysis. We have developed a novel, green, and economical procedure for Buchwald-type C–N cross-coupling of aryl chlorides and amines. This coupling method works under aerobic and solvent-free conditions and gives excellent yields of value-added N-arylated or N-alkylated products. [ABSTRACT FROM AUTHOR]

Pyrrole derivatives with C(2)-aryl substituents are an important and widespread class of heterocyclic compounds. Their synthesis can be accomplished using several strategic variants which usually entail either protection of the N–H functionality followed by the arylation, or a direct arylation. Although direct arylation is a preferable process due to a reduced number of synthetic steps, it often requires vigorous conditions or challenging reagents. To this synthetic repertoire, we add a novel method that is based on the dual role of the arylating agent. It serves as the nitrogen protecting group while also being involved in the arylation step. Deprotection as a final stage is carried out simultaneously utilising amines as reacting components. This approach ensures relatively mild conditions and exclusive C(2) selectivity yielding 2-arylpyrroles with the amide functionality. While aromatic amines are not suitable partners under studied conditions, most likely due to lower nucleophilicity, aliphatic amines, either primary or secondary, afford products in good yields. [ABSTRACT FROM AUTHOR]

Cyclopropyldiphenylsulfonium salt, a famous ylide precursor previously extensively employed in the preparation of cyclic compounds, has been successfully utilized as an efficient allylation reagent in this work. The copper-catalyzed reactions of cyclopropyldiphenylsulfonium trifluoromethanesulfonate with amines in the presence of an appropriate ligand provided the N -allylated products in good yields. Aliphatic/aromatic amines and primary/secondary amines were all converted under mild reaction conditions. This protocol was also applicable to N -functionalization of drug molecules, supplying the corresponding N -allylated compounds in satisfactory yields. The reaction, which showed good functional group tolerance with a wide range of substrates and excellent chemoselectivity, offers an interesting method for the synthesis of N -allyl amines. [ABSTRACT FROM AUTHOR]

Concise one-pot biarylamination of quinones with arylamines was developed to synthesize N -arylamine-functionalized p -iminoquinones derivatives. The approach employed AgOAc as the catalyst and (NH4)2 S2 O8 as the oxidant in the presence of 3-chlorophenylboronic acid, giving a series of N -arylamine-functionalized p -iminoquinone derivatives in moderate to good yields whereas reaction in the absence of the 3-chlorophenylboronic acid, gave a series of N -arylamine-functionalized 1,4-naphthoquinone derivatives. This catalytic approach represents a step-economic and convenient strategy for the difunctionalization of quinones. [ABSTRACT FROM AUTHOR]

We have developed an efficient iron-catalyzed one-pot reaction of tryptamines, ynones and nitroolefins, affording indole-tethered tetrasubstituted pyrroles in acceptable to good yields. Other aromatic and aliphatic amines can also be utilized in this process, delivering the corresponding highly functionalized tetrasubstituted pyrroles. Indolizino[8,7- b ]indole derivatives could be obtained through TFA-, TfOH- or Fe(OTf)3-mediated cyclizations via dearomatization of indole. Unexpected dibrominated products, 7,9-dibromo-6,11-dihydro-5 H -indolizino[8,7- b ]indoles, were formed when trimethylphenylammonium tribromide (PTAP) was employed as electrophilic cyclization promoter. [ABSTRACT FROM AUTHOR]

A tandem approach was developed for the efficient synthesis of substituted chromeno[4,3- b ]quinolines from arylamines and O -cinnamyl salicylaldehydes under metal-catalyst- and photosensitizer-free reaction conditions. Our protocol is based on an inexpensive I2 /DMSO system in which molecular iodine first acts as a Lewis acid to promote the formation of the corresponding imine bearing the alkene moiety; then, this species fulfills a second role by catalyzing an intramolecular aza-Diels–Alder cycloaddition to generate the respective tetrahydrochromenoquinoline as an intermediate. Finally, the dual behavior of DMSO as an oxidant and as a solvent proved crucial at this stage, allowing the regeneration of I2 and promoting the aromatization of the tetrahydrochromenoquinoline intermediates to yield the desired 7-aryl-6 H -chromeno[4,3- b ]quinolines. This protocol is mild and easy to perform, features high step-economy (tandem process) and provides a new access to biologically important nitrogen- and oxygen-containing heterocyclic molecules. [ABSTRACT FROM AUTHOR]

We present a base-mediated hydroamination protocol, using substoichiometric amounts of a hydrosilane and potassium tert -butoxide-, that operates under mild conditions at 30 °C. Many aryl- and heteroatom-substituted olefins as well as arylamines are tolerated, affording the desired products with complete regioselectivity. Preliminary mechanistic investigations reveal a non-radical pathway for hydroamination. A sequential remote hydroamination strategy involving an initial Fe-catalysed olefin isomerisation followed by our base-mediated hydroamination was also developed to directly access β-arylamines from terminal aliphatic alkenes. [ABSTRACT FROM AUTHOR]

Recently, intense efforts have been dedicated to the development of novel synthetic strategies to access aromatic amines due to their importance in the pharmaceuticals, agrochemicals, materials, and natural product areas. Although numerous transition-metal-catalyzed C–N formation strategies have been described for the preparation of aromatic amines in the past few decades, complementary methods under transition-metal-free conditions are still required. We present the recent advances in the exploration of innovative amination approaches via C(sp2)–O/C(sp2)–S bond cleavage in this review. 1 Introduction 2 Stoichiometric Base-Promoted Amination 3 Base-Catalyzed Amination 4 Photoredox-Catalyzed Amination 5 Acid-Promoted Amination 6 Conclusion and Perspectives [ABSTRACT FROM AUTHOR]

The use of tertiary amines as surrogates for secondary amines has prominent advantages in terms of stabilization and ease of handling. A Ni-catalyzed transamidation of N -acylsaccharins with tertiary aromatic amines is reported. By using tert -butyl hydroperoxide as the terminal oxidant, this reaction permits selective cleavage of the C(sp3)–N bonds of unsymmetrical tertiary aromatic amines depending on the sizes of the alkyl substituents. [ABSTRACT FROM AUTHOR]

An efficient protocol for the construction of valuable β-hydroxy aryl selenides from easily available arylamines, elemental selenium, and epoxides through a transition-metal-free radical process is described. A wide variety of β-hydroxy aryl selenides were obtained in good to excellent yields with excellent stereo- and regioselectivity. In this reaction, two C–Se bonds can be built along with the cleavage of a C–N and C–O bond, demonstrating the high step economy and efficiency of this approach. [ABSTRACT FROM AUTHOR]

A new method for the fast synthesis of diverse 4-aryl-6-cycloamino-1,3,5-triazin-2-amines was developed. The synthesis is performed under microwave irradiation in a one-pot manner from cyanoguanidine, aromatic aldehydes, and cyclic amines. Their three-component reaction in the presence of hydrochloric acid produced dihydrotriazines, which were then converted (without isolation) into the targeted compounds via aromatic dehydrogenation in the presence of alkali. The reaction tolerated various aromatic aldehydes (including heterocyclic) and cyclic amines. Crystal structures of two representative 4-aryl-6-morpholino-1,3,5-triazin-2-amines were established by X-ray crystallography. The results of preliminary biological screening identified potent antileukemic activity for 6-[3,4-dihydroisoquinolin-2(1 H)-yl]-4-phenyl-1,3,5-triazin-2-amine. [ABSTRACT FROM AUTHOR]

N -Aryl-1,2,3,4-tetrahydroisoquinolines are obtained via a convenient and short protocol with a broad range of substituents on both aromatic rings and high functional group tolerance. Starting from readily available ortho -brominated aromatic aldehydes and primary aromatic amines, condensation of these building blocks under reductive conditions gives N -aryl 2-bromobenzylamines. The C-3/C-4-unit of the tetrahydroisoquinoline is introduced using commercially available 2-ethoxyvinyl pinacolboronate under Suzuki conditions. Finally, the obtained crude ortho -ethoxyvinyl benzylamines are cyclized via an intramolecular reductive amination using the combination of triethylsilane/TFA to give the desired N -aryl-1,2,3,4-tetrahydroisoquinolines. [ABSTRACT FROM AUTHOR]

An efficient Cu-catalyzed synthesis of carbazole derivatives is reported, which proceeds by double C–N coupling reactions of 2,2′-dibromobiphenyl and amines in the presence of air. The reaction is robust, proceeds in high yields, and tolerates a series of amines including neutral, electron-rich, electron-deficient aromatic amines and aliphatic amines. [ABSTRACT FROM AUTHOR]

Herein we report the use of a soluble polymer support PEG-2000 on Pd-catalyzed reactions to improve the functionalization of aromatic amines and the synthesis of N-heterocycles. Compatibility of metal-catalyzed reactions for assembling privileged structures such as functionalized anilines were studied. PEG-supported anilines were found to be suitable substrates for Pd-catalyzed N-arylation, Sonogashira and Heck reactions. PEGylated substrates were prepared in yields up to 94%. This work consists on a proof of concept on the use of PEGylated anilines on Pd-catalyzed cross-coupling reactions. Indole core was attained in 82% and 62% yields, via two different routes. [ABSTRACT FROM AUTHOR]

The atom-efficient formation of amide bonds has emerged as a top-priority research field in organic synthesis, as amide bonds constitute the backbones of proteins and represent an important structural motif in drug molecules. Currently, the increasing demand for novel discoveries in this field has focused substantial attention on this challenging subject. Herein, the degradable 1,3,5-triazo-2,4,6-triphosphorine (TAP) motif is presented as a new condensation system for the dehydrative formation of amide bonds between diverse combinations of aromatic carboxylic acids and amines. The underlying reaction mechanism was investigated, and potential catalyst intermediates were characterized using31 P NMR spectroscopy and ESI mass spectrometry. [ABSTRACT FROM AUTHOR]

Phenols are considered as an ideal alternative to aryl halides as coupling partners in cross-coupling reactions. In the present work a copper-catalyzed cross-coupling of phenols with various aromatic and aliphatic amines for the synthesis of secondary aryl amines using dichloroimidazolidinedione (DCID) as a new and efficient activating agent has been developed. Substituted phenols were compatible with the standard reaction conditions. The two proposed mechanisms, which are based on the oxidation addition of copper with Ar-OMCID (MCID: Monochloroimidazolidinedione), are also discussed. [ABSTRACT FROM AUTHOR]

Carbenoid-based N–H insertions have undergone significant development with respect to C–N bond formation in recent years. However, the existing methods suffer from unstable starting materials, expensive metal catalysts and organic solvents. Herein, insertion of sulfoxonium ylides into arylamines under metal-free conditions has been developed. The method employs water as solvent at mild temperature and is amenable to the late-stage modification of structurally complex bioactive compounds. [ABSTRACT FROM AUTHOR]

A novel lanthanum triflate mediated conversion of N -benzyl-oxycarbonyl-, N -allyloxycarbonyl-, and N -trichloroethoxycarbonyl--protected amines into nonsymmetric ureas was discovered. In this study, lanthanum triflate was found to be an effective catalyst for preparing various nonsymmetric ureas from protected amines. A variety of protected aromatic and aliphatic carbamates reacted readily with various amines in the presence of lanthanum triflate to generate the desired ureas in high yields. This result demonstrated that this novel lanthanum triflate catalyzed preparation of ureas from Cbz, Alloc, and Troc carbamates can be employed for the formation of various urea structures. [ABSTRACT FROM AUTHOR]

The difunctionalization of ethyl α-diazoacetate (EDA) using silyl halides as a nucleophile and N , O -acetals as an electrophile under metal-free conditions is described. This process undergoes a novel three-component coupling (3-CC) reaction using EDA, which leads to a one-pot preparation of α-halo β-amino acid esters. Also, this protocol could be adapted to accept an electrophile composed of aromatic tertiary amines. In both 3-CC reactions, the key reaction intermediate is an iminium intermediate that can be easily and effectively generated either from N , O -acetals or from aromatic tertiary amines. [ABSTRACT FROM AUTHOR]

A green H2 O-promoted solvent-free hydroamination of electron-deficient terminal alkynes with amines has been developed. All secondary amines, including aliphatic and aromatic amines, gave the corresponding (E)-enamines in good to excellent yields, whereas primary aromatic amines afforded Z -configured products in moderate yields. Propiolates, propyn-1-ones, propynamides, and 1-(ethynylsulfonyl)-4-methylbenzene were explored in this Michael addition. [ABSTRACT FROM AUTHOR]

An effective method for the synthesis of polysubstituted 2-imidazoline derivatives via palladium-catalyzed cyclization of 2,3-allenyl amines with aryl iodides is described. This pure domino process allows the formation of new carbon–carbon and carbon–nitrogen bonds in a single synthetic operation. [ABSTRACT FROM AUTHOR]

Sulfonated reduced graphene oxide (SrGO) has displayed great potential as a solid acid catalyst due to its efficiency, cost-effectiveness, and reliability. In this study, SrGO was synthesized by the introduction of sulfonic acid-containing aryl radicals onto chemically reduced graphene oxide using ultrasonication. The SrGO catalyst was characterized by Fourier Transform Infrared (FTIR) spectroscopy, Raman spectroscopy, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and transmission electron microscopy (TEM). Further, SrGO was effectively utilized as a metal-free and reusable solid acid catalyst for the chemoselective N - t -Boc protection of various aromatic and aliphatic amines under solvent-free conditions. The N - t -Boc protection of amines was easily achieved under ambient conditions affording high yields (84–95%) in very short reaction times (5 min–2 h). The authenticity of the approach was confirmed by a crystal structure. The catalyst could be easily recovered and was reused up to seven consecutive catalytic cycles without any substantial loss in its activity. [ABSTRACT FROM AUTHOR]

In the selective N-arylation of amines or azoles with aryl halides-, methyl-α- d -glucopyranoside (MG) was found to function as a green ligand of copper powder. In addition, nitrogen heterocyclic amine compounds can also undergo the N-arylation coupling with heterocyclic aryl chlorides. This process allows access to a variety of aromatic amines and aryl azoles under mild reaction conditions, has good tolerance, and proceeds in moderate to high yield. [ABSTRACT FROM AUTHOR]

An efficient and metal-free coupling reaction has been developed that affords acetamides from the corresponding aryl amines and acetonitrile. This method tolerates a wide range of functional groups and is selective toward aryl amines. Preliminary mechanistic studies were conducted. [ABSTRACT FROM AUTHOR]

Herein, we report the natural ligand quebrachitol (QCT) as a promoter for a Cu(II) catalyst, which is highly effective for N-arylation of various amines and related aryl halides. A series of diarylamine derivatives were obtained in high yields by using diethylene glycol (DEG) as both ligand and solvent. The C–N coupling reactions proceed under mild conditions and exhibit good functional group tolerance. [ABSTRACT FROM AUTHOR]

Triazolopyridine-pyridine amine ligands are easily obtained by means of either thermal- or copper(II)-mediated reactions. Starting from a readily accessible iodo derivative of triazolopyridine-pyridine and different amines, this new family of compounds combines aromatic and aliphatic nitrogen atoms with promising coordinating properties. Furthermore, chemical derivatization of a new triazolopyridine-pyridine diamine compound, N 1-[6-([1,2,3]triazolo[1,5- a ]pyridin-3-yl)pyridin-2-yl]ethan-1,2-diamine, allows the preparation of several remote-pyridine-containing ligands. [ABSTRACT FROM AUTHOR]

Thanks to a highly active catalyst, the scope of the (cyclopentadienone)iron complex-promoted 'hydrogen-borrowing' (HB) amination has been expanded to secondary alcohols, which had previously been reported to react only in the presence of large amounts of co-catalysts. A range of cyclic and acyclic secondary alcohols were reacted with aromatic and aliphatic amines giving fair to excellent yields of the substitution products. The catalyst was also able to promote the cyclization of diols bearing a secondary alcohol group with primary amines to generate saturated N-heterocycles. [ABSTRACT FROM AUTHOR]

A comparative study of various widely used methods of reductive amination is reported. Specifically, such reducing agents as H2 , Pd/C, hydride reagents [NaBH4 , NaBH3 CN, NaBH(OAc)3 ], and CO/Rh2 (OAc)4 system were considered. For understanding the selectivity and activity of the reducing agents reviewed herein, different classes of starting materials were tested, including aliphatic and aromatic amines, as well as aliphatic and aromatic aldehydes and ketones. Most important advantages and drawbacks of the methods, such as selectivity of the target amine formation and toxicity of the reducing agents were compared. Methods were also considered from the viewpoint of green chemistry. [ABSTRACT FROM AUTHOR]

Asymmetric allylic amination of Morita–Baylis–Hillman (MBH) adducts with simple aromatic amines is successfully realized by nucleophilic amine catalysis. A range of substituted α-methylene-β-arylamino esters is accessed in moderate to high yields (up to 88%) and with excellent enantioselectivities (up to 97% ee). Inorganic fluorides are found to be able to improve the enantioselectivity of the allylic amination reaction. A pyrrole-2-carboxylate and a cyclic imide are also compatible with this catalytic system. A chiral 2,3-dihydroquinolin-4-one derivative is easily obtained from the allylic amination product. [ABSTRACT FROM AUTHOR]

A new efficient catalytic system for one-step synthesis of N-arylated amines, for example, an important intermediate, 4-ethyl- N -[(tetrahydrofuran-3-yl)methyl]aniline, is achieved by using different rhodium precursor and phosphorus ligands catalyzed hydroaminomethylation of aniline and its derivatives with heterocyclic and/or cyclic olefins. By screening the reaction parameters, the optimal reaction conditions are found as follows: methanol as a solvent, PPh3 as a ligand, [Rh(cod)2 ]BF4 as a catalyst precursor, a P/Rh ratio of 5:1, syngas pressure 4 MPa (H2 /CO = 3:1), 100 °C, 20 hours, and no additives. The conversion of aniline reaches >99% and the yield of N -[(tetrahydrofuran-3-yl)methyl]aniline is up to 99% using this catalytic system. Moreover, the reaction of aniline and various cyclic olefins is investigated under the optimal conditions, and excellent conversion and good yields are obtained. [ABSTRACT FROM AUTHOR]

Using NaBAr4 as an arylating agent, the formation of carbon- heteroatom bonds by a Cham-Lam cross-coupling reaction in the presence of catalytic copper(II) acetate monohydrate in acetonitrile at room temperature under air is described. The investigation of reaction scope suggests that several aliphatic and aromatic amines are compatible. In particular, the reaction of alkylamine and NaBAr4 proceeds smoothly to offer the corresponding products in good to excellent yields. [ABSTRACT FROM AUTHOR]

Efficient and versatile catalytic systems were developed for the N-methylation of both aliphatic and aromatic primary amines using methanol as the methylating agent. Iridium complexes bearing an Nheterocyclic carbene (NHC) ligand exhibited high catalytic performance for this type of transformation. For aliphatic amines, selective N,N-dimethylation was achieved at low temperatures (50-90 °C). For aromatic amines, selective N-monomethylation and selective N,N-dimethylation were accomplished by simply changing the reaction conditions (presence or absence of a base with an appropriate catalyst). These findings can be used to develop methods for synthesizing useful amine compounds having N-methyl or N,N-dimethyl moieties. [ABSTRACT FROM AUTHOR]

We developed an environmentally friendly iridium-catalyzed direct cyclization of aromatic amines with diols that generates the corresponding N-heterocyclic compounds with water as the sole by-product. Thus, under conditions of 165 °C for 18 hours, the direct cyclization of N-methylanilines with 1,3-propanediol by using an IrCl3 catalyst with rac-BINAP as a ligand in mesitylene afforded the corresponding tetrahydroquinoline derivatives with yields ranging from 73 to 83%. Under similar reaction conditions, direct cyclization of anilines with 1,3-propanediol produced the corresponding tetrahydrobenzoquinolizine derivatives with yields ranging from 26 to 76%. [ABSTRACT FROM AUTHOR]