Synthesis of α-indanones via intramolecular direct arylation with cyclopropanol-derived homoenolates

A palladium-catalysed, tandem cyclopropanol rearrangement and direct arylation approach for the synthesis of 1-indanones is reported. The reaction is generally high yielding, uses oxygen as the terminal oxidant and tolerates a range of functional groups on the aryl ring.     

Synthesis of aza-crown compounds by intramolecular cyclization of ω-amino acids

A method for the synthesis of aza-crown compounds by the intramolecular cyclization of -amino acids with subsequent reduction of the lactam to a macrocyclic amine was developed. 1,8-Diazacyclotetradecane and 1,8-dioxa-4,11-diazacyclotetradecane were synthesized in preparative yields. The structural assignments were made using the IR, ¹H and ¹³C NMR, and mass spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 247–255, February, 1992.     

Nickel-catalyzed intramolecular C–H arylation using aryl pivalates as electrophiles

This paper describes a method for nickel catalyzed intramolecular C–H arylation using aryl pivalates as electrophiles. The transformation is efficient for the synthesis of diverse electronically and sterically differentiated dibenzofurans. Additionally, the method could be expanded toward the synthesis of carbazoles. Preliminary mechanistic studies of the transformation are also described.     

Synthesis of new thioxanthenes by organocatalytic intramolecular Friedel–Crafts reaction

An efficient organocatalytic route has been developed to synthesize novel substituted thioxanthenes (2a–2v) starting from diaryl thioether alcohols (1a–1v) using the intramolecular Friedel–Crafts reaction. The starting materials were obtained in two stages via a coupling reaction followed by the Grignard reaction. In this study, we tried for the first time to use some organic Brønsted acids as organocatalysts (3a–3h) in the intramolecular Friedel–Crafts cyclization reaction of thioether alcohols. The synthesis of original substituted thioxanthenes was achieved within 15?minutes by using N-triflylphosphoramide (3h) with quantitative yields in THF at room temperature.     

Trace analysis of benzophenone-derived compounds in surface waters and sediments using solid-phase extraction and microwave-assisted extraction followed by gas chromatography–mass spectrometry

This study describes a procedure for determining eight benzophenone-derived compounds in surface waters and sediments. These include the pharmaceutical ketoprofen, its phototransformation products 3-ethylbenzophenone and 3-acetylbenzophenone, and five benzophenone-type ultraviolet (UV) filters. The proposed analytical method involves the pre-concentration of water samples by solid-phase extraction (SPE) and microwave-assisted extraction (MAE) of sediment samples followed by derivatization and analysis by gas chromatography–mass spectrometry. Different parameters were investigated to achieve optimal method performance. Recoveries of 91 to 96 % from water samples were obtained using HLB Oasis SPE cartridges, whereas MAE of sediments (30 min at 150 °C) gave recoveries of 80 to 99 %. Limits of detection were between 0.1 and 1.9 ng L^?1 for water samples and from 0.1 to 1.4 ng g^?1 for sediment samples. The developed method was applied to environmental samples and revealed the presence of UV filters in the majority of the surface waters with up to 690 ng L^?1 of 2-hydroxy-4-methoxybenzophenone. By contrast, ketoprofen (≤2,900 ng L^?1) and its degradation products (≤320 ng L^?1) were found in only two rivers, both receiving wastewater treatment plant effluents. Sediment analysis revealed benzophenone to be present in concentrations up to 650 ng g^?1, whereas concentrations of other compounds were considerably lower (≤32 ng L^?1). For the first time, quantifiable amounts of two ketoprofen transformation products in the aqueous environment are reported.     

Site-specific acid–base properties of pholcodine and related compounds

The acid–base properties of pholcodine, a cough-depressant agent, and related compounds including metabolites were studied by ¹H NMR-pH titrations, and are characterised in terms of macroscopic and microscopic protonation constants. New N-methylated derivatives were also synthesized in order to quantitate site- and nucleus-specific protonation shifts and to unravel microscopic acid–base equilibria. The piperidine nitrogen was found to be 38 and 400 times more basic than its morpholine counterpart in pholcodine and norpholcodine, respectively. The protonation data show that the molecule of pholcodine bears an average of positive charge of 1.07 at physiological pH, preventing it from entering the central nervous system, a plausible reason for its lack of analgesic or addictive properties. The protonation constants of pholcodine and its derivatives are interpreted by comparing with related molecules of pharmaceutical interest. The pH-dependent relative concentrations of the variously protonated forms of pholcodine and morphine are depicted in distribution diagrams.     

Synthesis of tricyclic compounds via sequential intramolecular Michael addition and alkylation of β-ketoester ynones

Base-catalyzed sequential intramolecular Michael addition and alkylation of cyclic β-ketoester ynones 1 (n = 1,2) produce the corresponding tricycles 3 via intermediate enone-anions 2.     

Pd-catalysed intramolecular regioselective arylation of 2-pyrones,pyridones, coumarins and quinolones by C–H bond functionalization

The intramolecular arylation of 2-pyrones, 2-pyridones, coumarins and quinolones is reported using Pd^II precatalyst sources without added phosphine ligands. The excellent yields and convenient reagents enables the formation of various analogues containing these moieties, and access to potential biologically active candidates. Stoichiometric studies were carried out to provide an insight into the oxidation addition step. A switch in regioselectivity, together with a hydrodebromination process, was observed in the case of a 3-bromo-2-pyrone.     

Synthesis of 5′-benzoyl-2′-hydroxychalcones and related flavonoid compounds

Summary 5 -Benzoyl-2 -hydroxychalcones were synthesized by the condensation of 5 -benzoyl-2 -hydroxyacetophenone with aromatic aldehydes in presence of an ethanolic solution of potassium hydroxide. Derivatives of 6-benzoylflavonoids were prepared from chalcones.     

Synthesis of 2′-hydroxychalcones and related compounds in interfacial solid-liquid conditions

A general synthetic method of 2′-hydroxychalcones and 2′-hydroxyphenyl-(2-alkylvynyl) ketones in interfacial solid-liquid conditions, is described. No secondary reactions were observed. The interfacial mechanism is discussed by means of the structure of active sites of solid.     

Synthesis of some new lignans and the mechanism of intramolecular nonphenolic oxidative coupling of aromatic compounds

Treatment of cis-1,4-diaryl-2,3-epoxy butane with 2,3-dichloro-5,6-dicyano-1,4-benzo-quinone(DDQ) in trifluoroacetic acid(TFA) gave dibenzocycloheptadienes by pinacol rearrangement and intramolecular oxidative coupling of the aryl groups. Meanwhile, the benzofuran analogues were also formed by the same method. These new lignans have potent CNS inhibitory activities. It has been proven that the method is particularly useful when applied to the substrates in which the ring substituents are electron donating. The structures of these products were identified by the MS, UV, IR, NMR spectra, and elemental and X-ray crystallographic analyses.     

Synthesis and antimicrobial activity of novel quinazolinone–thiazolidine–quinoline compounds

A series of 2-(2-chloroquinolin-3-yl)-5-((aryl)benzylidene)-3-(4-oxo-2-phenylquinazolin-3(4H)-yl)thiazolidin-4-ones (V)_1–12 have been synthesized. In order to establish optimization of different parameters of chemical transformation, that is the reaction pathway for each step and reaction conditions in the each step, in the present paper, different solvents and catalysts were used. The structures of the synthesized compounds were assigned on the basis of elemental analysis, IR, ¹H NMR and ¹³C NMR spectral data. All the newly synthesized compounds were screened against various strains of bacteria and fungi.     

A mild and efficient direct α-amination of β-dicarbonyl compounds using iodosobenzene and p-toluenesulfonamide catalyzed by perchlorate zinc hexahydrate

A direct α-amination of β-dicarbonyl compounds has been achieved by using iodosobenzene (PhIO) as an oxidant and p-toluenesulfonamide (TsNH(2)) as an aminating reagent in the presence of a catalytic amount of perchlorate zinc hexahydrate. The present amination reaction proceeds quickly at rt (<30 min needed for most tested substrates) to provide the corresponding α-N-tosylamido β-dicarbonyl compounds in high to excellent yields.     

Synthesis of 2-indanones by intramolecular insertion of α-diazoketones

The reaction of α-diazoketones from phenylacetic acid derivatives affords 2-indanones in good yield. Insertion into the aromatic CH bond was found to be favored over insertion into an aliphatic one.     

C–H arylation of triphenylene,naphthalene and related arenes using Pd/C

A highly selective arylation of a number of polyaromatic hydrocarbons (PAHs) with aryliodonium salts and Pd/C as the only reagent is reported. The first C–H functionalization of triphenylene is explored, and proceeds at the most sterically hindered position. This non-chelate assisted C–H functionalization extends the reactivity profile of Pd/C and provides controlled access to π-extended PAHs, an important aspect of work towards the preparation of nanographenes. Mechanistic studies suggest in situ formation of catalytically active insoluble nanoparticles, and that the reaction likely proceeds via a Pd(0)/Pd(ii) type reaction manifold.     

Triphyrin catalyzed direct C–H arylation of benzene with aryl halides

Transition-metal free direct C–H arylation of benzene with aryl halides was achieved by meso-aryl-substituted [14]triphyrins(2.1.1) catalysts in an air atmosphere. Various aryl halides underwent successful direct C–H arylation of benzene to give moderate to high yields of biaryls. A radical mechanism is proposed for this triphyrin catalyzed C–H arylation reaction.     

Synthesis and reactivity of enediyne–nucleobase hybrids: effect of intramolecular π-stacking

Three distinct classes of nucleobase-containing enediynes 1–9 with varying nature of the linker have been synthesized to explore the effect of π-stacking interaction in accelerating the rate of Bergman cyclization (BC). Chemical reactivity study, both experimental and computations demonstrated the important role that aromatic π-stacking interactions between the appended nucleobases within an enediyne frame play in lowering the activation barrier of Bergman cyclization.