Novel synthesis of 2-chloroquinolines from 2-vinylanilines in nitrile solvent

2-Vinyl- or heteroaryl-substituted anilines were reacted with diphosgene in acetonitrile solution via a reactive imidoyl moiety to afford the corresponding 2-chloroquinolines. Facile syntheses of nine 2-chloroquinoline derivatives from several anilines and their postulate mechanism is described. The postulate mechanism of 2-chloroquinoline formation via imidoyl moiety as a good leaving group shows that the reaction consists of the following three steps: (1) generation of phenylisocyanate, (2) quinoline ring formation, and (3) chlorination on C2 position of quinoline.     

Catalytic asymmetric synthesis of N-substituted tetrahydroquinoxalines via regioselective Heyns rearrangement and stereoselective transfer hydrogenation in one pot

N-Substituted tetrahydroquinoxalines (37 examples) were step-economically obtained in good yield (<97%) and ee (<99%) with readily available substrates. The reaction proceeds through an interesting regioselective Heyns rearrangement/enantioselective transfer hydrogenation in one pot. The substrate scope and the reaction mechanism were systematically investigated.

N-Substituted tetrahydroquinoxalines were step-economically obtained in good yield and ee with readily available substrates.     

Novel synthesis of 4-halo-3-hydroxy-2-pyrone: one pot rearrangement-cyclization reaction by magnesium halide

Treatment of acetonide protected 4,5-dihydroxy-2-chloroglycidic ester or its rearrangement product, the acetonide protected 4,5-dihydroxy-3-chloro-2-oxo ester, with magnesium halides gave 4-halo-3-hydroxy-2-pyrone in excellent to reasonable yields in one pot. The mechanism of this novel one pot rearrangement-cyclization reaction is also proposed.     

One-pot conversion of phenols to anilines via Smiles rearrangement

A convenient one-pot synthesis of phenols to anilines using 2-chloroacetamide/K₂CO₃/DMF system catalyzed by KI via Smiles rearrangement has been described. The synthesis of extensive amino aromatic products from phenols containing electron withdrawing group, has been performed in moderate to excellent yields to demonstrate the potentiality of this method in bio-medicinal and pharmaceutical applications.     

Solution-phase parallel synthesis of 4,6-diaryl-pyrimidine-2-ylamines and 2-amino-5,5-disubstituted-3,5-dihydro-imidazol-4-ones via a rearrangement

The reaction of chalcones and guanidine was investigated in the presence of an oxidizing agent. Depending on the order of the addition either a 4,6-diaryl-pyrimidine-2-ylamine or 2-amino-5,5-disubstituted-3,5-dihydro-imidazol-4-one was obtained. The structures of the imidazolinones were elucidated by NMR spectroscopy and X-ray crystallography and for its formation a mechanism was proposed.     

Efficient stepwise and one pot three-component synthesis of 2-amino-4-(2-oxo-2H-chromen-3-yl)thiophene-3-carbonitriles

Environmentally benign conditions have been developed for the synthesis of 2-amino-4-(2-oxo-2H-chromen-3-yl)thiophene-3-carbonitriles (3) starting from 3-acetyl-2H-chromen-2-one (1) through the intermediacy of 2-(1-(2-oxo-2H-chromen-3-yl)ethylidene)malononitrile (2) using the Knoevenagel condensation followed by the Gewald reaction. Alternatively, 3 could also be prepared in a one pot method by treating equimolar amounts of 1, malononitrile, and elemental sulfur. The merits of this preparation are mild reaction conditions, easy work-up procedure, and good yields.     

Novel approach towards one pot stereospecific synthesis of carbohydrate derived substituted imidazolines

A simple synthetic approach has been developed towards one pot synthesis of 2-imidazolines under mild acidic conditions from N-acetyl glucosamine via reductive amination followed by dehydrative cyclization. Synthetic studies were explored in detail with different amines and sugar derivatives. While the conversion was good, the corresponding substituted imidazolines were obtained in moderate yields.     

Smiles rearrangement of polyfluoro substituted 2-acetylaminodiaryl ethers

Polyfluoro substituted 2-acetylaminodiaryl ethers of the type Ar_FOC₆H₄NHAc-o (II) that contain in the fluorinated ring an acceptor group, like analogs of the NH₂ group, undergo on heating in DMF the Smiles rearrangement accompanied by partial migration of the acetyl group and cyclization (in case of ethers (IIa, b)) to phenoxazine derivatives. In the case of heating in DMF, the rate constant of the rearrangement of diphenyl ether (IIa) is by an order of magnitude lower than the rate constant of the rearrangement of its analog with an NH₂ group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 850–854, April, 1990.     

Benzoxazinone synthesis via Passerini–Smiles couplings

Benzoxazinones are easily prepared using Passerini–Smiles couplings of o-nitrophenol derivatives. Palladium-catalyzed flow-hydrogenation of adducts gives aniline derivatives that cyclize into benzoxazinones on treatment with trifluoroacetic acid.     

A facile one pot synthesis of 1-alkylbenzimidazoline-2-thiones

Reactions of benziraidazoline-2-thione with alkyl halides in the presence of sodium naphthalenide in tetra-hydrofuran at room temperature under a nitrogen atmosphere afforded 1-alkyl-2-alkylthiobenzimidazoles in excellent yields, which underwent a bond cleavage between S and C of alkyl group to give excellent yields of 1-alkylbenzimidazoline-2-thiones by the treatment with an additional amount of sodium naphthalenide.     

Novel synthesis of 2-amino-3-hetaryl-4(5H)-oxothiophenes

3-Cyano-3-hetaryl-2-oxopropyl thioacetates were obtained by the acylation of hetarylacetonitriles with acetylmercaptoacetyl chloride. Their reaction with amines led to the formation of 2-amino-3-hetaryl-4(H)-oxothiophenes. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 680–685, May, 2006.     

Asymmetric synthesis of 2-chloroaziridines via a diastereoselective nucleophilic dichloromethylation and N-alkylation in one pot

A diastereoselective nucleophilic dichloromethylation between the N-tert-butanesulfinyl imines and dichloromethyllithium was developed. A series of 2-chloroaziridines with excellent yields and dr values were obtained via this nucleophilic addition and N-alkylation in one pot. On the basis of X-ray crystallography experiment, the predicting model for this diastereoselective transformation was provided.     

Silica chloride (SiO2-Cl) catalyzed one pot synthesis of 2,3-disubstituted-thiazolidin-4-one

Abstract

In this paper, we report one-pot, three-component cyclo condensation of an aldehyde, an amine and thioglycolic acid to form 2,3-disubstituted-thiazolidin-4-one by using supported protic acid (Silica Chloride: SiO₂-Cl) catalyst. The catalyst SiO₂-Cl is compatible with a variety of aldehydes (aryl/heteroaryl) and the aromatic amines affording 2,3-disubstituted-thiazolidin-4-one analogs in 72–89% yields. Moreover, the supported catalyst was recycled several times without significant loss of catalytical activity     

Stereocontrolled synthesis of Z-dienes via an unexpected pericyclic cascade rearrangement of 5-amino-2,4-pentadienals

Donor-acceptor dienes known as Zincke aldehydes, which derive readily from the ring-opening reactions of pyridinium salts with secondary amines, undergo a fascinating thermal rearrangement reaction to afford Z-alpha,beta,gamma,delta-unsaturated amides with excellent stereoselectivity. Efficient, stereocontrolled access to Z-trisubstituted alkenes with two different substitution patterns is possible in three steps beginning with the appropriately substituted pyridine derivative. Preliminary studies have shown that both the amide and the monosubstituted alkene termini can be selectively functionalized. Ease of access, generality of scope, and facile product manipulation render this process attractive for the synthesis of complex polyenes.     

Synthesis of substituted pyrimidine using ZnFe2O4 nanocatalyst via one pot multi-component reaction ultrasonic irradiation

A highly efficient, eco-friendly, recyclable heterogeneous ZnFe₂O₄ nanocatalyzed synthesis of 2-amino-4-substituted 1,4-dihydrobenzo[4,5]imidazo[1,2-a]pyrimidine-3-carbonitrile (4a-j) derivatives via one pot multicomponent reaction of benzimidazole ( 1 ), substituted aromatic aldehyde ( 2a-j ) and malononitrile ( 3 ) under ultrasonic irradiations. Significance of this synthetic approach is short reaction time, easy handling, simplicity, efficiency, high yield, and recoverable catalyst.     

Pyrrolo-dihydropteridines via a cascade reaction consisting of iminium cyclization and O-N Smiles rearrangement

The reactions of 5-pyrrolyl-pyrimidinyloxyacetaldehyde or methyl ketone with primary amines yielded hydroxymethylpyrrolopteridine derivatives via a cascade of iminium cyclization and O-N Smiles rearrangement. The present cascade exhibited a different profile compared to the previously reported ones, which consisted of N-N Smiles rearrangement. Lewis acid (TiCl₄) under carefully controlled conditions was employed to suppress the competing formation of imine dimers to give the desired heterocycles. A plausible mechanism involving the iminium cyclization and Smiles rearrangement is proposed. This methodology has been used to generate a series of 6-hydroxymethylpyrrolo[1,2-f]pteridine derivatives with potential biological activities.     

Microwave-assisted one-pot synthesis of benzo[b][1,4]thiazin-3(4H)-ones via Smiles rearrangement

The synthesis of benzo[b][1,4]thiazin-3(4H)-one derivatives in a simple and efficient method from the one-pot reaction of substituted 2-chlorobenzenthiols, chloroacetyl chloride, and primary amines via Smiles rearrangement under microwave irradiation gave high yields (65-92%) of the products with short reaction time (15-20 min).     

Microwave-assisted one-pot synthesis of benzo[b][1,4]oxazin-3(4H)-ones via Smiles rearrangement

An efficient method for the synthesis of benzo[b][1,4]oxazin-3(4H)-ones via Smiles rearrangement using a microwave-assisted one-pot, three-step reaction has been developed. Various benzo[b][1,4]oxazin-3(4H)-ones are obtained in good yields (55-86%) from the corresponding substituted 2-chlorophenols and primary amines in short reaction time (18-40 min).     

A one pot synthesis of annulated carbazole analogs

A ZnBr₂-mediated arylation of N-protected 2/3-bromomethylindoles containing an electron-deficient malonylidene unit with arenes at 80 °C led to the formation of arylated products, which on unprecedented 1,5-sigmatropic rearrangement followed by electrocyclization and subsequent aromatization with loss of diethylmalonate furnished the corresponding annulated carbazoles in reasonable yields.