Selectively reductive amination of levulinic acid with aryl amines to N-substituted aryl pyrroles

Synthesizing nitrogen(N)-containing molecules from biomass derivatives is a new strategy for production of this kind of chemicals.Herein,for the first time we present the synthesis of N-substituted aryl pyrroles via reductive amination/cyclization of levulinic acid(LA)with primary aromatic amines and hydrosilanes(e.g.,PMHS)over Cs F,and a series of N-substituted aryl pyrroles could be obtained in good to excellent yields at 120○C.The mechanism investigation indicates that the reaction proceeds in two steps:the cyclization between amine and LA occurs first to form intermediate 5-methyl-N-alkyl-1,3-dihydro-2H-pyrrolones and their isomeride(B),and then the chemo-and region-selective reduction of intermediates take place to produce the final products.This approach for synthesis of N-substituted aryl pyrroles can be performed under mild and green conditions,which may have promising applications.

Synthesis of Calix[4]pyrroles: A Class of New Molecular Receptor

Calix[4]pyrroles, as a class of new molecular receptor in the area of supramolecular chemistry, have displayed interesting anion and neutral substrate binding properties. In this paper, several new calix[4]pyrrole macrocycles were synthesised and characterized.

Yb(OTf)_3-catalyzed synthesis of pyrroles under solvent-free conditions

A Yb（OTf）3-catalyzed approach for the synthesis of pyrroles under solvent-free conditions was achieved, which could afford the desired products with yields ranged from moderate to excellent.

A new method for the synthesis of N-substituted pyrroles

An unexpected reaction of 10-bromomethyl-12-oxocalanolide A（2） with primary amine was demonstrated and studied. Consequentially,a new method for the preparation of N-substituted pyrroles starting fromγ-halo-α,β-unsaturated ketone was presented.

A convenient synthesis of pyrroles catalyzed by acidic resin under solvent-free condition

A convenient and effective Paal-Knorr condensations of 2,5-hexanedione with most amines have been carried out at room temperature under solvent-free condition.Macroporous strongly acidic styrol resin(D001) as a novel,efficient,cost-effective,and reusable solid acid catalyst for the synthesis of pyrroles under the same conditions.The pyrroles were obtained in high yields in short reaction times.

Synthesis of Pyrroles and Condensed Pyrroles as Anti-Inflammatory Agents with Multiple Activities and Their Molecular Docking Study

We herein disclose a series of novel pyrrole derivatives as well as fused pyrrolopyridines 6a,b and 7a,b, pyrrolopyrazoles 8a, b, pyrrolo[2,3-d]pyrimidine derivatives 10a-d, 12a,b, 14a,b, 18a,b, 20a,b, 21a,b, 22a,b, 23a,b, 24a,b, 31a,b, 36a,b, 40a,b, pyrrolo[1,2,6]thiadiazine derivatives 19a,b, pyrrolotriazolopyrimidines 25a,b, 26a,b, 27a,b and 28a,b, pyrrolo[2,3-d][1,2,3]triazine derivatives 32a,b and pyrrolo[2,3-d][1,3]oxazine derivatives 39a,b as novel compounds. All compounds were evaluated for their anti-inflammatory, analgesic (compared to the reference drug Indomethacin) and antimicrobial activities (compared to the reference drug Ampicillin and Fluconazole). Compounds 4d, 5b-d, 6a,b, 9c,d, 10d, 12ab, 13b, 19a,b, 21b, 23b, 31a,b, 38b and 40a were found to be the most active anti-inflammatory drugs exhibiting potency ranging from 1 - 1.01 compared to the reference drug indomethacin. In addition to docking study of these highly active twenty compounds against the active site of cyclooxygenase-2 enzyme (COX-2), among the tested compounds, compounds 5d, 9d, 11b, 12a, 13b and 32a showed multiple activities;anti-inflammatory, analgesic and anti-bacterial activities.

A Facile and Efficient Synthesis of Substituted Pyrroles by Three Component Coupling Reaction of Amines, Aldehydes and Nitroalkanes

A facile and efficient synthesis of highly substituted pyrroles has been achieved by a one-pot three-component coupling reaction of aldehyde, amine and nitroalkane by triethyl orthoformate.

Alkylations of Resorcarenes and Calix[4]pyrroles in Phase Transfer Catalytic Systems

Resorcarens 1a-b (R'=Ph, p-MeOC6H4) were fully alkylated with alkyl iodides or bromides in TEBA/KOH/DMF solid-liquid PTC process with 63-82% yields, whereas the three calix[4]pyrroles 3a-b (2R= 2Me, (CH2)(4), (CH2)(5)) were alkylated with alkyl iodides in TBAB/ 50%NaOH/ CH2Cl2 liquid-liquid PTC system with lower yields (10-38%).

New Subsidiary Interaction Mode of Counteranions with the Periphery Cavity of Calix[4]pyrroles Binding with the Anion Subunits

The solution binding properties of calix[4]pyrroles with anion （as tetraalkylammonium salts） were investigated using UV-Vis spectroscopic techniques. The obvious red-shift of absorption maximum band of calix[4]pyrrole in EtOH in the presence of the tetramethylammonium （TMA^＋） salts or tetraethylammonium （TEA^＋） salts were observed, due to the charge-transfer interactions between the electron-rich pyrrole rings of calix[4]pyrroles and TMA^＋ or TEA^＋ cation subunit. The results indicated that calix[4]pyrrole receptors, which link the anionic species through multiple hydrogen bonding interactions, can use the periphery cavity for selectively binding cation subunits by cation-π charge-transfer interaction. The subsidiary interaction mode helps to further stabilize the calix[4]pyrrole-anion complex.

Visible Light-Induced[3+2]Annulation Reaction of Alkenes with Vinyl Azides:Direct Synthesis of Functionalized Pyrroles

A photocatalytic[3+2]annulation of alkenes with vinyl azides was developed under irradiation by visible light in the presence of organic dye photocatalysts.Broad substrate scope and high functional group tolerance were demonstrated by more than 50 examples.The reaction provides a novel and efficient method for the synthesis of polyfunctionalized pyrroles under very mild metal-free conditions without other additives.

Recent advances in the construction of axially chiral arylpyrroles

Catalytic enantioselective preparation of axially chiral molecules has gained considerable interest over the past decades, due to their numerous applications in bioactive molecules, natural products, pharmaceuticals, materials, ligands, and catalysts. Compared with the well-established synthetic approaches for six-membered axially chiral skeletons, methodologies directed towards five-membered axially chiral compounds are relatively rare. Among these, axially chiral arylpyrroles are especially important structural motifs with wide utility, and the atroposelective synthesis of them is highly desirable. In recent years, novel strategies have been developed based on transition-metal catalysis and organocatalysis. This review summarizes the recent achievements in atroposelective preparation of arylpyrroles, by emphasizing the synthetic methods for each axially chiral framework, reaction mechanisms, and applications.

Au-catalyzed neighboring hydroxymethyl group directed cycloaddition of alkyne with diazadienes:Synthesis of polysubstituted pyrroles

Polysubstituted pyrroles are very important scaffolds in many bioactive natural products and synthetic pharmaceuticals.Here,a new gold-catalyzed cycloaddition of alkynes with azadienes to access tetrasubstituted pyrroles is demonstrated.The neighboring hydroxylmethyl group serves a very important directing group through an addition/cycloaddition/elimination cascade.Diverse polysubstituted pyrroles were synthesized in good yields under mild conditions in one step,and tricyclic pyrrole containing heterocycles were easily obtained through derivatization.

Bifurcated Rhodaelectro-catalyzed C−H Activation for the Synthesis of Pyrroles and Lactones

While electrocatalyzed alkyne annulations of arenes represent a powerful strategy for the assembly of heteroaromatic motives,electrochemical C(sp2)−H activations of alkenes remain scarce.Herein,a strategy for the rhodaelectro-catalyzed function-alization of enamides is presented for the efficient construction of pyrroles using electricity as a sustainable oxidant.Moreover,the tuning of the solvent system allowed a fascinating switch in chemoselectivity,which is not possible with traditionally used chemical oxidants,giving rise to lactone architectures.The rhoda-electrocatalysis features a broad scope as well as high regio-and chemoselectivities.

Recent advances in the syntheses of pyrroles

The pyrrole moiety is an important structural motif in functional materials,natural products,and pharmaceuticals.More and more synthetic strategies toward pyrroles have emerged,where various efficient building blocks are developed and these synthons enable the syntheses of pyrroles with different numbers of components.However,no review specifically summarizes the syntheses of pyrroles according to the type and number of employed building blocks.To aid researchers to design appropriate substrates for pyrrole synthesis,herein we summarized the advances in pyrrole syntheses and classified these reactions into four categories according to the number of employed components,which may shed light on developing more efficient synthetic methods toward substituted pyrroles.

Theoretical characterization of the adsorption configuration of pyrrole on Si(100)surface by x-ray spectroscopy

The possible configurations of pyrrole absorbed on a Si(100)surface have been investigated by x-ray photoelectron spectroscopy(XPS)and near-edge x-ray absorption fine structure(NEXAFS)spectra.The C-1s XPS and NEXAFS spectra of these adsorption configurations have been calculated by using the density functional theory(DFT)method and fullcore hole(FCH)approximation to investigate the relationship between the adsorption configurations and the spectra.The result shows that the XPS and NEXAFS spectra are structurally dependent on the configurations of pyrrole absorbed on the Si(100)surface.Compared with the XPS,the NEXAFS spectra are relatively sensitive to the adsorption configurations and can accurately identify them.The NEXAFS decomposition spectra produced by non-equivalent carbon atoms have also been calculated and show that the spectral features vary with the diverse types of carbon atoms and their structural environments.

Facile access to chiral 1-pyrrolines through Rh-catalyzed enantioselective partial hydrogenation of unprotected simple pyrroles

Highly enantioselective Rh-catalyzed partial hydrogenation of unprotected simple 2-alkyl-5-aryl-disubstituted pyrroles has been successfully developed,generating a series of chiral 1-pyrroline derivatives generally with excellent results(95%-99%yields,91%-96%ee).Moreover,2,5-aryl-1H-pyrroles were hydrogenated well in high yields and good enantioselectivities.This efficient protocol features easily accessible substrates,wide substrate scope,well functional group compatibility,commercially available rhodium precursor and chiral ligand.It provides a versatile route to access chiral 1-pyrroline derivatives that are of great importance in organic synthesis and pharmaceutical chemistry.

Synthesis of polysubstituted pyrroles via a gold(Ⅰ)-catalyzed tandem three-component reaction at room temperature

A gold(Ⅰ)-catalyzed three-component reaction of β-nitrostyrenes with 1,3-dicarbonyl compounds and primary amines to form polysubstituted pyrroles has been developed at room temperature in ethanol.The key advantages of the three-component reaction are the mild reaction conditions and environmentally safer solvent.

Research on Inorganic Anion Recognition of Calix[4]pyrroles and Dipyrrylmethanes by Capillary Zone Electrophoresis

Capillary electrophoresis （CE） can separate charged and neutral substances with high speed and efficiency. In this paper, utilizing meso-octamethylcalix[4]pyrrole, meso-tetraspirocyclohexylcalJx[4]pyrrole, bimethyl bi（2-pyrryl）- methane and 1,1-bi（2-pyrryl）cyclohexane as additives in capillary zone electrophoresis （CZE） electrolyte, their recognition ability to inorganic anions was discussed. The dipyrrylmethanes have better recognition ability than others. Their effects on separation of seven normal inorganic anions by CZE were studied.

Palladium-catalyzed cyclization of 1-alkynyl-8-iodonaphthalene and double isocyanides for the synthesis of acenaphtho[1,2-b]pyrroles

A palladium-catalyzed formal[2+2+1]cyclization of 1-alkynyl-8-iodonaphthalene with double isocyanides is developed herein.The transformation worked well to produce a series of 7 H-acenaphtho[1,2-b]pyrrole with a broad reaction scope.Isocyanides play a dual role in the reaction.One is a C1 building block,and another is used as C1 N1 component.In the process,the[2+2+1]cyclization involves imidoylation,regioselective addition of imidoylpalladium species into alkyne,double imidoylation,and another addition of the resulting imidoylpalladium species into imine bonds.