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Rapeseed meal (RSM) is a by-product of rapeseed oil extraction and is a rich source of bioactive compounds, including proteins and antioxidants. This study compared two methods for extracting antioxidants from RSM: conventional ethanol Soxhlet extraction and supercritical CO2 extraction. These procedures were applied to both native RSM and RSM after protein removal to evaluate their bio-compound composition and potential applications. HPLC-DAD, NMR, and GC/MS analyses revealed a rich polyphenolic profile in the extracts, including the presence of sinapic acid. The concentration of sinapic acid varied depending on the extraction method used. The anti-radical activity of the extracts was also analysed using the DPPH assay, which confirmed the potential of RSM as a source of antioxidants for use in cosmetics, food, and pharmaceutical formulations.

Fruit seeds belonging to the pomegranate cultivar "Granata" were subjected to extraction and oily component analysis, with the aim of obtaining information about their composition. The presence of conjugated isomers of linolenic acid (CLNA isomers) in the oily phase extracted from the seeds gives a high added value to this part of the fruit, which is too often considered and treated as waste. The separated seeds were subjected to a classic Soxhlet extraction with n-hexane or extraction with supercritical CO2, assisted by ethanol. The resulting oils were evaluated by H-1 and C-13-NMR and AP-MALDI-MS techniques. Differences in the triacylglycerols composition, with particular regard to punicic acid and other CLNA content, were studied in depth. Results showed the prevalence of punicic acid in the triacylglycerol mixture up to the 75%, with clear preponderance in the extract by supercritical fluids. Consequently, other CLNA isomers are, altogether, two-fold less represented in the supercritical extract than in the Soxhlet one. The two oily residues were subjected to solid phase extraction (SPE) and to HPLC-DAD analysis for the polyphenolic isolation and characterization. In addition to HPLC analysis, which showed different content and composition, DPPH analysis to evaluate the antiradical potential showed that the extract obtained with supercritical CO2 was much more active.

A gold-catalyzed protocol to obtain functionalized 3H-pyrrolo [1,2,3-de] quinoxalines from suitable substituted N-alkynyl indoles has been proposed. The mild reaction conditions were revealed to be compatible with different functional groups, including halogen, alkoxyl, cyano, ketone, and ester, allowing the isolation of title compounds with yields from good to high. A reaction mechanism has been proposed, and theoretical calculations have been provided to rationalize the final step of the hypothesized reaction mechanism. As quinoxaline-containing polycyclic compounds, this class of molecules may represent a valuable template in medicinal chemistry and material science.

The synthesis of 2,3-dihydropyrazino[1,2-a]indol-4(1H)-ones from the sequential reaction of amino acid methyl esters with readily available indole-2-ylmethyl acetates is described. The reaction proceeds in situ under basic conditions of highly unstable and reactive 2-alkylideneindolenines followed by Michael-type addition of a-amino acid methyl esters/intramolecular cyclization.

A palladium-catalyzed domino approach toward synthetically challenging phenanthrene derivatives has been developed. The procedure involves a sequence of oxidative homocoupling, cyclization, and oxidation starting from deoxybenzoin derivatives halogenated in the ortho position. Good assembly efficiency and good functional group tolerance have been observed with yields from moderate to excellent. A plausible reaction mechanism has been proposed based on experimental results and literature data.image

The aim of this work was to develop innovative and sustainable extraction, concentration, and purification technologies aimed to recover target substances from corn oil, obtained as side stream product of biomass refineries. Residues of bioactive compounds such as carotenoids, phytosterols, tocopherols, and polyphenols could be extracted from this matrix and applied as ingredients for food and feeds, nutraceuticals, pharmaceuticals, and cosmetic products. These molecules are well known for their antioxidant and antiradical capacity, besides other specific biological activities, generically involved in the prevention of chronic and degenerative diseases. The project involved the development of methods for the selective extraction of these minor components, using as suitable extraction technique solid phase extraction. All the extracted and purified fractions were evaluated by NMR spectroscopic analyses and UV–Vis spectrophotometric techniques and characterized by quali-quantitative HPLC analyses. TPC (total phenolic content) and TFC (total flavonoid content) were also determined. DPPH and ABTS radical were used to evaluate radical quenching abilities. Acetylcholinesterase (AChE), amylase, glucosidase, and tyrosinase were selected as enzymes in the enzyme inhibitory assays. The obtained results showed the presence of a complex group of interesting molecules with strong potential in market applications according to circular economy principles.

The gold-catalyzed cyclization of 2,2-bis(3-arylprop-2-yn1-yl)malonic acid has been proposed as an efficient approach to substituted 3,8-dibenzyl-2,7-dioxaspiro[4.4]nonane-1,6-diones. The reaction proceeds smoothly in mild reaction conditions to give the desired products in quantitative yields in the presence of variously substituted starting materials. In addition, the synthesis of gamma-arylidene spirobislactone bearing different substituents on the two aromatic rings has been achieved. This kind of compound could be of great interest in pharmaceutical science given the widespread presence of this scaffold in bioactive natural and synthetic products.

The plants of the Moraceae family are producers of a great variety of polyphenolic natural products. Among these, the Diels-Alder type adducts (DAAs) are endowed with a unique cyclohexene scaffold, since they are biosynthesized from [4+2] cycloaddition of different polyphenolic precursors such as chalcones and dehydroprenyl polyphenols. To date, more than 150 DAAs have been isolated and characterized from Moraceous and related plants. The main source of DAAs is the mulberry root bark, also known as "Sang-Bai-Pi" in Traditional Chinese Medicine, but they have also been isolated from root bark, stem barks, roots, stems or twigs, leaves, and callus cultures of Moraceous and other related plants. Since 1980, many biological activities of DAAs have been identified, including anti-HIV, antimicrobial, anti-inflammatory, and anticancer ones. For these reasons, natural DAAs have been intensively investigated, and a lot of efforts have been made to study their biosynthesis and to establish practical synthetic access. In this review, we summarized all the updated knowledge on biosynthesis, chemoenzymatic synthesis, racemic and enantioselective total synthesis, and biological activity of natural DAAs from Moraceous and related plants.

A straightforward assembly of polysubstituted 1,2-dihydro-3H-pyrrolo[1,2-a]indol-3-ones through a domino palladium-catalyzed reaction of indol-2-ylmethyl acetates with 1,3-dicarbonyl derivatives is described. The key role of the features of the 1,3-dicarbonyls on the reaction outcome has been explored. The employment of 2-methylcyclohexan-1,3-dione as the dicarbonyl source could allow further challenging indole nucleus functionalizations.

The synthesis of (aminomethyl), (tosylmethyl), and (aryloxymethyl) indoles starting from indolylmethylacetates and N, O, and S soft nucleophiles has been developed. ESI-MS and IR multiple-photon dissociation (IRMPD) spectroscopy analyses confirm the reaction proceeds through a conjugate addition of the nucleophile to 2-alkylideneindolenines and 3-alkylideneindoleninium.

Hydroarylation reactions play a pivotal role in organic chemistry due to their versatility and efficiency. In the last 10 years, the scientific production around this reaction has been very high, but in its asymmetric version, the results are less. In this mini review, selected literature examples are considered to draw attention to directions of the asymmetric hydroarylation reaction mediated by transition metal catalysts. The selected works were grouped in two main sections. In the first, we reported examples relating the narrower definition of hydroarylation, namely the metal-catalyzed processes where inactivated aryl moiety undergoes a direct functionalization via insertion of an unsaturated compound. In the second part, hydroarylation reactions take place with the use of pre-activated aryl substrates, usually aryl-iodides or aryl-boronated.

The functionalized 3,4-dihydroquinolin-2-one nucleus has been assembled in good to high yields through the sequential reaction of readily available N-Ts-o-aminobenzyl alcohols with 5-substituted Meldrum's acid derivatives under mild basic conditions. Highly diastereoselective synthesis of 3-substituted-4-phenyl-1-tosyl-3,4-dihydroquinolin-2(1H)-ones was accomplished from N-(2-(hydroxy(phenyl)methyl)phenyl)-4-methylbenzenesulfonamide under the same reaction conditions. Regarding the reaction mechanism, we hypothesized that the formation of dihydroquinolones proceeds through the in situ generation of aza-o-QMs followed by conjugate addition of enolate/cyclization/elimination of acetone and CO2

The field of organocatalysis is expanding at a fast pace. Its growth is sustained by major stimuli, such as the effort toward an understanding of the mechanisms of reaction and catalytic processes in general, the elucidation of basic properties leading to stereocontrol and the search for broad applicability and scalability of the synthetic methodology. This paper reports a thorough study based on ESI-MS spectrometry of amino-organocatalyzed model reactions under different experimental conditions. Off-line reaction monitoring of mixtures containing different catalytic systems, by ESI-MSn showed the presence of several putative intermediate species, either in their protonated or sodiated forms. In addition, enantioselective chromatography of crude reactions provides the stereochemical outcome of asymmetric reactions. The bulk of the data collected offers a clue of the intricate pathways occurring in solution for the studied reactions.

This study describes diversity-oriented synthesis of 2,2,3-substituted-2,3-dihydroquinolin-4(1H)-ones vs. functionalised quinoline or N-alkenylindole derivatives through Brønsted acid mediated or Lewis acid catalyzed sequential reactions of 2-alkynylanilines with ketones. In particular, a series of challenging quinolin-4-one derivatives are prepared with good functional group tolerance in an atom-economical fashion by using p-toluenesulfonic acid monohydrate as a promoter of the reaction of ketones with 2-alkynylanilines in EtOH at reflux, while the same starting materials give the corresponding 4-substituted quinolines in toluene at 110 °C both in the presence of p-toluenesulfonic acid monohydrate as the promoter and FeCl3 as the catalyst. The divergent formation of N-alkenylindole derivatives occurs by switching to the use of ZnBr2 as the catalyst under the same reaction conditions. Conversely, only 4-methylsubstituted quinoline derivatives were isolated by reacting 2-ethynylanilines and/or 2-trimethylsylilanilines with ketones in all examined cases. This journal is

The presence of stereogenic elements is a common feature in pharmaceutical compounds, and affording optically pure stereoisomers is a frequent issue in drug design. In this context, the study of the chiral molecular recognition mechanism fundamentally supports the understanding and opti-mization of chromatographic separations with chiral stationary phases. We investigated, with molecular docking, the interactions between the chiral HPLC selector Whelk-O1 and the stereoisomers of two bioactive compounds, the antiviral Nevirapine and the anticonvulsant Oxcarbazepine, both char-acterized by two stereolabile conformational enantiomers. The presence of fast-exchange enantiomers and the rate of the interconversion process were studied using low temperature enantioselective HPLC and VT-NMR with Whelk-O1 applied as chiral solvating agent. The values of the energetic barriers of interconversion indicate, for the single enantiomers of both compounds, half-lives suffi-ciently long enough to allow their separation only at critically sub-ambient temperatures. The chiral selector Whelk-O1 performed as a strongly selective discriminating agent both when applied as a chiral stationary phase (CSP) in HPLC and as CSA in NMR spectroscopy.

Plants represent a rich source of structurally diverse secondary metabolites, which can be exploited in the development of new clinically important compounds. Indeed, due to their biodiversity, medicinal plants represent the largest library of compounds that has ever existed. To date less than 1% of this vast biodiversity has been exploited in drug discovery, due to several factors, including the lack of an appropriate multidisciplinary perspective. Here we review the successful application of computer-aided methods in screening a unique and high-diversity in house collection library composed of around 1000 individual natural products, isolated mainly from indigenous plants collected in biodiversity-rich countries, especially of the tropics and subtropics, and enlarged with their semi-synthetic and synthetic derivatives, as well as plant material extracts, up to around 2000 components. During the last ten years, the in house library has provided several lead compounds that have been developed, and in some cases patented, as anticancer and antimicrobial agents. The main classes of the library are described, including (but not limited to) alkaloids, terpenoids, Diels-Alder-type adducts, isoflavones, chalcones, and cannabinoids. The main focus is on the chemical characteristics and biological activity of these identified compounds, with particular attention being given to those currently under patent or in the preclinical phase. We also assess the use of computer-aided methods in screening this unique and diverse in house collection of natural products that, over the last ten years, has provided some lead compounds that have been developed, and in some cases patented, as anticancer and antimicrobial agents. Finally, this review highlights the potential use of plant food extracts as a source of nutraceuticals and functional foods. The multidisciplinary approach described herein may further motivate research groups involved in natural product chemistry to potentially ben

A regioselective gold (I)-catalyzed approach for the construction of polycyclic chromene cores has been developed. The reaction proceeds in good to excellent yields under mild condition with a broad range of substrates providing a simple and efficient tool for the synthesis of pyranochromene derivatives. Moreover, the regiochemical control of the annulation of unsymmetrically substituted propargylic ethers has been investigated focusing on electronic/steric effects of the ligands of gold complexes as well as on the electronic effects of the groups on the aromatic rings.

Background: In recent years, the use of ferritins as nano-vehicles for drug delivery is taking center stage. Compared to other similar nanocarriers, Archaeoglobus fulgidus ferritin is particularly interesting due to its unique ability to assemble-disassemble under very mild conditions. Recently this ferritin was engineered to get a chimeric protein targeted to human CD71 receptor, typically overexpressed in cancer cells. Results: Archaeoglobus fulgidus chimeric ferritin was used to generate a self-assembling hybrid nanoparticle hosting an aminic dendrimer together with a small nucleic acid. The positively charged dendrimer can indeed establish electrostatic interactions with the chimeric ferritin internal surface, allowing the formation of a protein-dendrimer binary system. The 4 large triangular openings on the ferritin shell represent a gate for negatively charged small RNAs, which access the internal cavity attracted by the dense positive charge of the dendrimer. This ternary protein-dendrimer-RNA system is efficiently uptaken by acute myeloid leukemia cells, typically difficult to transfect. As a proof of concept, we used a microRNA whose cellular delivery and induced phenotypic effects can be easily detected. In this article we have demonstrated that this hybrid nanoparticle successfully delivers a pre-miRNA to leukemia cells. Once delivered, the nucleic acid is released into the cytosol and processed to mature miRNA, thus eliciting phenotypic effects and morphological changes similar to the initial stages of granulocyte differentiation. Conclusion: The results here presented pave the way for the design of a new family of protein-based transfecting agents that can specifically target a wide range of diseased cells. Graphic abstract: [Figure not available: see fulltext.].

Bioactive peptides are increasingly used in clinical practice. Reversed-phase chromatography using formic or trifluoroacetic acid in the mobile phase is the most widely used technique for their analytical control. However, sometimes it does not prove sufficient to solve challenging chromatographic problems. In the search for alternative elution modes, the dynamic electrostatic repulsion reversed-phase was evaluated to separate eight probe peptides characterised by different molecular weights and isoelectric points. This technique, which involves TBAHSO4 in the mobile phase, provided the lowest asymmetry and peak width at half height values and the highest in peak capacity (about 200 for a gradient of 30 min) and resolution concerning the classic reversed-phase. All analyses were performed using cutting-edge columns developed for peptide separation, and the comparison of the chromatograms obtained shows how the dynamic electrostatic repulsion reversed-phase is an attractive alternative to the classic reversed-phase.

An alternative Au(I)-catalyzed synthetic route to functionalized 1,2-dihydroquinolines is reported. This novel approach is based on the use of N-ethoxycarbonyl protected-Npropargylanilines as building blocks that rapidly undergo the IMHA reaction affording the 6-endo cyclization product in good to high yields. In the presence of N-ethoxycarbonyl-N-propargyl-metasubstituted anilines, the regiodivergent cyclization at the ortho-/para-position is achieved by the means of catalyst fine tuning.

The toolbox of medicinal chemists includes the 1,4-benzodiazepine scaffold as a “privileged scaffold” in drug discovery. Several biologically active small molecules containing a 1,4-benzodiazepine scaffold have been approved by the FDA for the treatment of various diseases, with most of them being used for their psychotropic effects. The therapeutic potential of 1,4-benzodiazepines has stimulated the interest of synthetic chemists in developing new synthetic strategies to a range of substituted analogues for biological evaluation. A structural variation of the classical benzodiazepine skeleton is observed e.g. in alprazolam, midazolam, and related benzodiazepines, which contain a 1,2,4-triazole or an imidazole ring fused to the benzodiazepine core. Irrespective of the presence of the fused heterocyclic ring, the seven-membered diazepine ring is far from planar, and its shape resembles a twist chair. Then, the unsymmetrical substitution pattern around the seven membered cycle renders these molecules chiral, as they lack any reflection-type symmetry element. However, chirality of this molecules is labile at room temperature, becausea simple ring flipping process converts one enantiomer into the other, and 1,4-benzodiazepines exist as a mixture of rapidly interconverting conformational enantiomers in solution at or near room temperature. Physical separation of the interconverting enantiomers of diazepam and of other related 1,4-benzodiazepin-2-ones can be accomplished by low temperature HPLC on chiral stationary phases (CSPs). If the HPLC column is cooled down to temperatures where the interconversion rate is sufficiently low, compared to the chromatographic separation rate, distinct separated peaks can be observed, provided the CSP is sufficiently enantioselctive. The apparent rate constants for the on-column enantiomerization and the corresponding free energy activation barriers were obtained by simulation of exchange-deformed HPLC profiles using a computer program b

Antibiotic resistance is now considered a worldwide problem that puts public health at risk. The onset of bacterial strains resistant to conventional antibiotics and the scarcity of new drugs have prompted scientific research to re-evaluate natural products as molecules with high biological and chemical potential. A class of natural compounds of significant importance is represented by alkaloids derived from higher plants. In this review, we have collected data obtained from various research groups on the antimicrobial activities of these alkaloids against conventional antibiotic-resistant strains. In addition, the structure-function relationship was described and commented on, highlighting the high potential of alkaloids as antimicrobials.

Fully ripe fruits and mature leaves of Elaeagnus angustifolia were harvested and analyzed by means of analytical and biological tests to better comprehend the chemical composition and therapeutic/nutraceutical potential of this plant. Fruits and leaves were dried and the obtained powders were analyzed to study their color character and (via headspace gas chromatography) describe the chemical profile. Subsequently, they were submitted to a chloroform–methanol extraction, to a hydroalcoholic extraction procedure assisted or not by microwaves, and to an extraction with supercritical CO2, assisted or not by ethanol as the co-solvent, to detect the polyphenolic and the volatile content. The resulting extracts were evaluated in terms of chlorophyll and carotenoid content, polyphenolic content, volatile fraction, total phenolic content, total flavonoid content, antioxidant activity, radical scavenging activity, and enzymatic inhibition activity. The results confirmed the correlation between the chemical composition and the high antioxidant potential of leaf extracts compared to the fruit extracts in terms of the phenolic and pigment content. A promising effect against tyrosinase emerged for all the extracts, suggesting a therapeutic/nutraceutical use for this plant. Conversely, the volatile content from both natural matrices was similar.

A straightforward approach to the synthesis of the challenging 12-arylindolo[1,2- c ]quinazolin-6(5 H)-ones through the palladium-catalyzed direct arylation of N -benzyl and NH-free [1,2- c ]quinazolin-6(5 H)-ones with aryl halides is described.

The gold-catalyzed hydroamination of 2-(arylethynyl)pyridines with anilines affords stereoselectively Z-enamine products with excellent regioselectivity. The reaction proceeds with moderate to excellent yields and accommodates a diverse range of functional groups on alkynes (ether, bromo, trifluoromethyl, acetyl, and carbomethoxy) and anilines (ether, bromo, chloro, and carbethoxy). The stereochemistry of the obtained enamines is complementary to that reported in previous studies. A plausible explanation for the observed selectivity was attained by means of NMR experiments.

Regioselective access to 10-substituted-2H,8H-pyrano[2,3-f]chromen-2-ones through the gold-catalyzed intramolecular hydroarylation of readily available 7-(prop-2-yn-1-yloxy)-2H-chromen-2-one derivatives at their C-8 congested position was investigated by tuning the electronic and steric properties of the ligand on the gold complex. On the other hand, the combination of the JohnPhosAu(MeCN)SbF6 catalyzed intramolecular hydroarylation of 8-iodo-7-(prop-2-yn-1-yloxy)-2H-chromen-2-one derivatives followed by selective palladium/formate C-I reduction allows for the exclusive formation of 2H,8H-pyrano[3,2-g]chromen-2-one regioisomers. The development of these two protocols provides versatile synthetic tools required for exploring the biological activities of these new pyranocoumarin derivatives.

An efficient, new copper-catalyzed approach to the construction of the multisubstituted imidazo[1,2- a ]pyridine skeleton from N -(2-pyridinyl)enaminones has been developed.

This work aims at elucidating the mechanism and kinetics of hydrolysis of GANT61, the first and most-widely used inhibitor of the Hedgehog (Hh) signalling pathway that targets Glioma-associated oncogene homologue (Gli) proteins, and at confirming the chemical nature of its bioactive form. GANT61 is poorly stable under physiological conditions and rapidly hydrolyses into an aldehyde species (GANT61-A), which is devoid of the biological activity against Hh signalling, and a diamine derivative (GANT61-D), which has shown inhibition of Gli-mediated transcription. Here, we combined chemical synthesis, NMR spectroscopy, analytical studies, molecular modelling and functional cell assays to characterise the GANT61 hydrolysis pathway. Our results show that GANT61-D is the bioactive form of GANT61 in NIH3T3 Shh-Light II cells and SuFu−/− mouse embryonic fibroblasts, and clarify the structural requirements for GANT61-D binding to Gli1. This study paves the way to the design of GANT61 derivatives with improved potency and chemical stability.

A straightforward one-pot approach to the synthesis of challenging 12-arylindolo[1,2- c ]quinazolin-6(5 H)-ones is described. Starting from readily available o -(o -aminophenylethynyl)trifluoroacetanilides, palladium-catalyzed aminoarylation of the triple bond with ArI, ArBr, and ArN 2+ BF 4- is followed by cyclization of the resulting N -trifluoroacetyl-2-(o -aminophenyl)-3-aryl indole. This sequential reaction provides the title compounds by means of a rare elimination of trifluoromethane.

An efficient strategy for the synthesis of 6-unsubstituted indolo[1,2-c]quinazolines is described. The Pd-catalyzed reaction of o-(oaminophenylethynyl) trifluoroacetanilides with Ar-B(OH)2 afforded 2-(o-aminophenyl)-3-arylindoles, that were converted to 12-arylindolo[1,2-c]quinazolines by adding dimethylformamide dimethyl acetal (DMFDMA) to the reaction mixture after extractive work-up. This reaction outcome is different from the previously reported Pd-catalyzed sequential reaction of the same substrates with Ar-I, Ar-Br and ArN2+BF4-, that afforded 12-arylindolo[1,2-c]quinazolin-6(5H)-ones. Moreover, 12-unsubstituted indolo[1,2-c]quinazolines can be obtained both by reacting 2-(o-aminophenyl)indoles with DMFDMA or by sequential Pd-catalyzed reaction of o-(o-aminophenylethynyl)aniline with DMFDMA.

2-Substituted 3-aroylquinolin-4(1H)-ones, prepared through a palladium-catalyzed carbonylative cyclization of N-(2-iodoaryl)enaminones, proved to inhibit efficiently the Hedgehog pathway through direct antagonism of the wild-type and drug-resistant form of the Smoothened receptor. Notably, these compounds repressed the Hh-dependent growth events and the proliferation of tumor cells with aberrant activation of the Hh pathway, which plays a crucial role in development and tumorigenesis.

A simple, straightforward palladium-catalyzed approach to 2-(aminomethyl)-3-arylindoles from 3-(o -trifluoroacetamidoaryl)-1-propargylic alcohols, amines, and aryl iodides has been developed..

The gold-catalyzed reaction of o-phenylendiamine with propargylic alcohols affords 1,5-benzodiazepines bearing different substituents on the 2 and 4 positions. The method allows even for the selective preparation of 4-substituted 1,5-benzodiazepine derivatives.

A facile and general approach to the synthesis of 2,5,7-trisubstituted indoles from readily available 2-bromo-6-iodo-4-substituted and 2-bromo-4-chloro-6-iodoanilines is reported. The assembly of the indole rings is accomplished via a one-pot Sonogashira cross-coupling with terminal alkynes followed by a palladium-catalyzed cyclization step. The functionalization at C7 and at C5 (with indoles bearing a chloro substituent at C5) is carried out by alkynylations, Suzuki-Miyaura cross-couplings, and Buchwald-Hartwig C-N bond forming reactions. One-pot protocols for the synthesis of 2,5,7-trisubstituted indoles from 2-aryl-7-bromo-5-chloroindoles as well as from 2-bromo-4-chloro-6-iodoaniline are also described.

Free NH 2-(aminomethyl) indoles have been prepared via copper-catalyzed cyclization of 3-(ortho-trifluoroacetamidophenyl)-1-propargylic alcohols in the presence of primary or secondary amines. The synthesis has been developed into a simple and very efficient domino three-component Sonogashira cross-coupling/cyclization/substitution process that, omitting the isolation of 3(ortho-trifluoroacetamidophenyl)-1-propargylic alcohols, provides access to this class of compounds by treating 2-iodotrifluoroacetanilides, propargylic alcohols, and primary or secondary amines with a copper/palladium catalyst system.

Free NH 2-substituted 3-arylindoles have been prepared usually in good to high yields through the palladium-catalyzed reaction of readily available 2-alkynyltrifluoroacetanilides with arylboronic acids under oxidative conditions. The reaction tolerates a variety of useful functional groups both in the arylboronic acid and in the alkyne, including chloro, formyl, and ester groups.

A novel copper-catalyzed approach to benzils from readily available deoxybenzoins under neutral conditions using air as the oxidant has been developed. The reaction tolerates a variety of useful substituents including chloro, bromo, iodo, keto, ester, and cyano groups. © Georg Thieme Verlag Stuttgart, New York.

A novel palladium-catalyzed approach to 2-amino ketones from arylpropargylic carbonates bearing neutral, electron-rich, and electron-poor aromatic rings and cyclic secondary amines containing useful functional groups such as cyano, chloro, and bromo substituents has been developed. © 2012 The Royal Society of Chemistry.

The palladium-catalyzed cyclization of 2-(2-bromoaryl)-3-arylindoles provides a new versatile approach to dibenzo[a,c]carbazoles. The reaction tolerates a variety of useful substituents including chloro, nitro, ether, cyano, keto, and ester groups. © 2012 The Royal Society of Chemistry.

Allylic sulfones are excellent precursors of aryl sulfones via a new Pd-catalyzed domino sequence involving in situ generation of sulfinate anions and subsequent cross-coupling with aryl -iodides or bromides. © Georg Thieme Verlag Stuttgart · New York.