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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]

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]

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]

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]

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]

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]

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]

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]

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]

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]

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]

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 describe herein the palladium-catalyzed aminocarbonylation of nitrogen-containing heterocycles with aniline derivatives using molybdenum hexacarbonyl as a CO solid source, expanding the scope of the limited examples. This method is compatible with a variety of substitutions on the aniline moiety. The simple reaction conditions include easily available Pd(dppf)Cl2 catalyst, DBU as base in DMF at 120 °C for 3 hours in sealed tube thereby leading to the isolation of 21 compounds with yields ranging from 18 to 82%. We also show that double aminocarbonylation reactions are possible in satisfactory yields regarding both coupling partners. [ABSTRACT FROM AUTHOR]

We describe herein the palladium-catalyzed aminocarbonylation of nitrogen-containing heterocycles with aniline derivatives using molybdenum hexacarbonyl as a CO solid source, expanding the scope of the limited examples. This method is compatible with a variety of substitutions on the aniline moiety. The simple reaction conditions include easily available Pd(dppf)Cl2 catalyst, DBU as base in DMF at 120 °C for 3 hours in sealed tube thereby leading to the isolation of 21 compounds with yields ranging from 18 to 82%. We also show that double aminocarbonylation reactions are possible in satisfactory yields regarding both coupling partners. [ABSTRACT FROM AUTHOR]

A convenient method for N-arylethylation of aromatic amines and heterocycles under mild reductive conditions was developed using (2-methoxyvinyl)(hetero)arenes as building blocks and triethylsilane/ trifluoroacetic acid as reducing agent. This protocol is compatible with numerous functional groups, and aliphatic amines are inert due to protonation. [ABSTRACT FROM AUTHOR]

Tertiary cyclic N-arylamines react with nitromethane in the presence of the tert-butyl hydroperoxide (T-HYDRO)/t-BuOK system to give β-nitroamines in up to 90% yield. When TMSCN is used in place of nitromethane, α-aminonitriles are obtained in up to 96% yield. The method is suitable for several unactivated cyclic arylamine substrates. These transformations are rationalized considering the formation of the corresponding iminium ion intermediates via an initial electron transfer process. [ABSTRACT FROM AUTHOR]

A novel, simple, and highly efficient method has been designed for the synthesis of ω-substituted arylbiurets in a one-pot reaction. The primary features of this protocol include readily available starting materials, an easy work-up procedure, and yields of 51 to 87%. ω-Substituted arylbiurets can be selectively prepared with an excess of potassium cyanate (KOCN). However, use of an excess of glacial acetic acid (AcOH) switches the reaction towards the formation of N-monosubstituted urea. [ABSTRACT FROM AUTHOR]

Herein, a synthetic approach using selective transition-metalcatalyzed cross-coupling reactions to thermally crosslinkable OLED materials based on vinyl-functionalized arylamines is reported. In a modular approach, 9,9-dialkyl-2,7-diiodo-9H-fluorene underwent a selective Ullmann cross-coupling reaction with bromo-substituted-diphenylamines to give 9,9-dialkyl-2,7-bis(bromo-substituted-diphenylamino)-9H-fluorenes that underwent end-functionalization by the Suzuki- Miyaura reaction using potassium vinyltrifluoroborate to give the corresponding 9,9-dialkyl-2,7-bis(vinyl-substituted-diphenylamino)-9H-fluorenes. Novel meta-functionalized materials were synthesized, which are difficult to prepare by traditional synthetic pathways. The thermal behavior of the compounds was investigated by DSC measurements, indicating a lower thermal sensitivity of the meta-substituted materials than their para-functionalized analogues. [ABSTRACT FROM AUTHOR]

The arylation of aromatic diamines with arylhydrazine hydrochlorides was achieved in reasonable yields. This new and simple reaction occurred at room temperature in air using an inexpensive base. This transformation seems to proceed via a homolytic aromatic substitution (HAS) mechanism. The synthesized aromatic diamines are used as raw materials for polyimides, including important aerospace materials, for example, Kapton®. [ABSTRACT FROM AUTHOR]

The synthesis of a series of novel quinoline fused imidazo[ 4,5-c]quinolines was accomplished by a simple, efficient, iodine- dimethyl sulfoxide (I2-DMSO) promoted sequential oxidative cross coupling followed by intramolecular cyclization of pyridoimidazole arylamines and carbonyl compounds in a one-pot reaction. Simple reaction conditions, no metal catalyst, no additives, no ligand, selective product formation and high yields are the advantages of this method. [ABSTRACT FROM AUTHOR]

The reaction of a 2-pyridinone-based acid fluoride with the N–TMS derivatives of different weakly nucleophilic heteroaryl/arylamines in acetonitrile containing catalytic fluoride ion provides a clean, efficient and simple means to access a diverse range of polar di(hetero) arylamide structures. This amide bond forming protocol is readily amenable to the parallel synthesis of compound libraries. [ABSTRACT FROM AUTHOR]

A novel reductive N-methylation protocol under acidic conditions with the TTT (1,3,5-trioxane-triethylsilane-trifluoroacetic acid) system is disclosed. This method is highly specific for aromatic amines and several N-heterocycles (indoles and annulated analogues, phenoxazine, phenothiazine), insensitive to steric hindrance, and compatible with a wide range of functional groups. Further the N-methylation step can be combined with an in situ N-Boc deprotection. Compounds in which the nucleophilicity of the NH group is eliminated by protonation under the reaction conditions (aliphatic amines, azaarenes of noteworthy basicity) are inert. In several examples, it was demonstrated that the TTT system is complementary to other N-methylation protocols. [ABSTRACT FROM AUTHOR]

A transition-metal-free, C-N bond-formation reaction between tertiary amines and aryl halides is reported. Under the optimal conditions, various aromatic and aliphatic tertiary amines react with aryl halides, including iodides, bromides, and chlorides, to give monoaminated products, N,N-dialkylanilines and N-alkyl-N-arylanilines, in good to high yields. Based on the experimental results, the reaction is believed to occur via an aryne intermediate derived from the aryl halide. [ABSTRACT FROM AUTHOR]

An efficient approach to 16 examples of polyfunctionalized isochromeno[4,3-b]indol-5(1H)-one derivatives, obtained in 60-85% yield and with excellent regioselectivity, has been developed through a domino reaction of 2,2-dihydroxyindene-1,3-dione with aromatic amines under microwave irradiation. The atom- and step-economy and scope make this reaction a powerful tool for assembling polyheterocyclic scaffolds of general chemical and biomedical interest. [ABSTRACT FROM AUTHOR]

A novel strategy for aromatic trifluoromethylation by converting amino into trifluoromethyl groups via a Sandmeyer-type reaction is reported. The transformation involves diazotization of the aromatic amines with tert-butyl nitrite and hydrochloric acid to form aryldiazonium chlorides, followed by trifluoromethylation with trifluoromethylsilver at low temperature. Various readily available aromatic amines are smoothly converted under mild conditions. [ABSTRACT FROM AUTHOR]

A biomass-based, metal- and ligand-free assembly of Naryl- 1,4-benzoxazin-3-ones from methyl 3-dehydroshikimate (3- MHDS), involving aliphatic to aromatic transformation followed by C-O and C-N forming reactions, is presented. A variety of N-aryl- 1,4-benzoxazin-3-ones were efficiently synthesized in a one-pot consecutive manner under microwave conditions. [ABSTRACT FROM AUTHOR]

Direct preparation of tertiary amines in which two substituents are aromatic is described. In the presence of either the inorganic base sodium tert-butoxide or the sterically hindered organic base diisopropylethylamine, the alkylation of secondary diarylamines is achieved smoothly. In contrast to methods previously reported in the literature, this procedure is high-yielding and does not require the use of transition-metal catalysts or functional-group-intolerant hydride reductants. [ABSTRACT FROM AUTHOR]

Aromatic azides are formed in high yield from arenediazonium tosylates and sodium azide in water at room temperature or from aromatic amines via diazotization in the presence of p-TsOH. Besides being experimentally simple, these methods do not require any metal catalysis and provide clean products without purification. [ABSTRACT FROM AUTHOR]

An improved palladium-catalyzed system is established for the synthesis of 3,4-dihydro-3-oxo-2H-1,4-benzoxazines from less reactive ethyl 2-(2-chlorophenoxy)alkanoates and aryl amines under controlled microwave heating, employing 2-dicyclohexylphosphino- 2',4',6'-triisopropylbiphenyl (XPhos) as the ligand. Moreover, a high-yielding, three-component reaction protocol is disclosed for the efficient one-pot synthesis of 3,4-dihydro-3-oxo- 2H-1,4-benzoxazines from 2-halophenols, ethyl 2-bromoalkanoates, and aryl amines. Microwave heating at high temperature is necessary to achieve high yields with 2-chlorophenol. A wide range of substrates is tolerated affording the desired products in good to excellent yields. [ABSTRACT FROM AUTHOR]

A simple and efficient method was developed for the synthesis of V-aroyl-V'-arylguanidines under mild conditions by an unexpected demethylation-addition cascade reaction of readily available V-cyanoimidates with aryl amines. Moreover, 1-aryl-2- aminoquinazolin-4(1#)-ones and 2-(arylamino)quinazolin-4(3H)- ones can also be prepared by selective cyclization reactions of (2- fluorobenzoyl)- or (2-nitrobenzoyl)guanidines, respectively. This method provided two attractive strategies for the preparation 2-aminoquinazolinones derivatives from inexpensive reactants. [ABSTRACT FROM AUTHOR]

A simple, one-pot, phosgene-free approach to a series of unsymmetrical 2-pyridyl ureas starting from 2-aminopyridine and various aromatic amines is reported for the first time. The procedure employs inexpensive selenium as the catalyst, and carbon monoxide (instead of phosgene) as the carbonyl reagent. The products are ob-tained in moderate to good yields via selenium-catalyzed oxidative cross-carbonylation of the substrate amines in the presence of oxy-gen. The selenium functions as a phase-transfer catalyst and can be recovered easily and reused without any significant degradation of its catalytic activity. [ABSTRACT FROM AUTHOR]

Treatment of 2-chloro-N-cyclopropylacetamide with phenols gave the corresponding 2-aryloxy-N-cyclopropylacetamides, which on treatment with a base gave the corresponding Ncyclopropylanilines. [ABSTRACT FROM AUTHOR]