Copper-catalyzed sulfenylation of pyrroles with disulfides or thiols: directly synthesis of sulfenyl pyrroles

We present here the synthesis of sulfenyl pyrroles by copper-catalyzed sulfenylation of pyrroles with organic disulfides or thiols. The direct sulfenylation of pyrroles with organic disulfides has been accomplished in the presence of 3 mol % of CuI in DMSO at 110 °C under air atmosphere. In the other hand, sulfenylation of pyrroles with thiols were performed in the same solvent and temperature, however it is necessary 5 mol % of CuI and nitrogen atmosphere. Using these protocols we were able to produce 2-sulfenyl pyrroles in good to excellent yields and with high selectivity without use of any ligand or additive.     

Direct intramolecular arylation of unactivated arenes: application to the synthesis of aporphine alkaloids

The direct intramolecular C-H arylation of unactivated arenes is a viable strategy for the synthesis of aporphine alkaloids. These reactions occur with 3 to 5 mol% catalyst and generate the aporphine skeleton in up to 99% yield.     

Direct synthesis of imines from gem-dibromomethylaryl derivatives: application to unsymmetrically substituted bipyridine frameworks

An efficient methodology for the one-pot synthesis of imines is described starting from gem-dibromomethylaryl compounds and primary amines. The synthesis was applied to various aliphatic mono- and polyamines as well as to electron-rich anilines. The protocol was extended to 6-bromo-5'-dibromomethyl-2,2'-bipyridine to afford the corresponding imines. With n-propyl- and n-decylamine, further conversion, in three steps, to the corresponding 6-carboxy-5'-alkylaminomethyl-2,2'-bipyridine derivatives was selectively achieved, providing new tridentate ligands that may find interesting applications for the complexation of lanthanide(III) cations in their anionic or zwitterionic form.     

Direct C-glycosylation of organotrifluoroborates with glycosyl fluorides and its application to the total synthesis of (+)-varitriol

A mild, stereoselective, and quick approach to accessing alkynyl and alkenyl C-glycosides via BF(3)·Et(2)O promoted coupling of organotrifluoroborates and glycosyl fluorides is reported. The application of this method was further demonstrated by the concise and efficient total synthesis of (+)-varitriol in only seven steps.     

Fluorescent core-shell polymer particles containing luminophore dyes: synthesis and optical response to acetone

Monodisperse dye-containing crosslinked particles are promising for application in novel optical chemical sensors due to their intrinsic sensitivity. However, preparation of these particles in aqueous media still remains a challenge, since luminophores inhibit radical processes or else cannot embed into polymer chains because of difference in monomer reactivity ratios. In this work, novel dye-containing monodisperse crosslinked particles were prepared and characterized. In order to obtain dye-containing monodisperse crosslinked particles, we studied seed copolymerization of styrene in the presence of divinylbenzene. The influence of nature and concentration of the used comonomers and co-solvents on shape, size distributions and surface characteristics of the particles formed was investigated. Shapes and diameters of the particles were analyzed by DLS, TEM and SEM. The data of SEM and optical spectroscopy studies demonstrated that the synthesized particles were able to self-assemble into thin-film three-dimensional ordered structures. Finally, the structures under study are promising for development of sensor devices with optical response to acetone.     

Photoredox-catalyzed sulfenylation/cyclization of N-aryl-N-tosylpropargylamine with disulfide: A concise route to 3-phenylthioquinoline

A facile and novel protocol for one-pot synthesis of 3-phenylthioquinoline derivates via visible-light induced tandem cyclization of N-aryl-N-tosylpropargylamine with disulfides was developed. This unprecedented method, involving CS bond formation, detosylation and aromatization, afforded the desired products in a broad substrate scope under mild conditions.     

Direct amino acid-catalyzed cascade biomimetic reductive alkylations: application to the asymmetric synthesis of Hajos-Parrish ketone analogues

A direct amino acid-catalyzed chemo- and enantioselective process for the double cascade synthesis of highly substituted 2-alkyl-cyclopentane-1,3-diones, 2-alkyl-3-methoxy-cyclopent-2-enones and Hajos-Parrish (H-P) ketone analogs is presented via reductive alkylation chemistry. For the first time, we have developed a single-step alkylation of cyclopentane-1,3-dione with aldehydes/ketones and a Hantzsch ester through an organocatalytic reductive alkylation strategy. A direct combination of amino acid-catalyzed cascade olefination-hydrogenation and cascade Robinson annulations of cyclopentane-1,3-dione, aldehydes/ketones, a Hantzsch ester and methyl vinyl ketone furnished the highly functionalized H-P ketone analogues in good to high yields and with excellent enantioselectivities. Many of the reductive alkylation products have shown direct applications in pharmaceutical chemistry.     

Direct synthesis of ester-containing indium homoenolate and its application in palladium-catalyzed cross-coupling with aryl halide

An efficient method for the synthesis of ester-containing indium homoenolate via a direct insertion of indium into β-halo ester in the presence of CuI/LiCl was described. The synthetic utility of the indium homoenolate was demonstrated by palladium-catalyzed cross-coupling with aryl halides in DMA with wide functional group compatibility.     

Palladium mediated spiroketal synthesis: application to pheromone synthesis

Stereospecific Stille coupling reactions of 2-metallo-dihydropyrans with Z-vinyl iodo alcohols and subsequent cyclisation provides rapid access to 1,7-dioxaspiro[5.5]undecane family of spiroketals.     

Proline-catalyzed aldol reactions of acyl cyanides with acetone: an efficient and convenient synthesis of 1,3-diketones

The aldol-type addition of acetone towards (un)substituted benzoyl, heteroarylcarbonyl or α,β-unsaturated acyl cyanides was efficiently catalyzed by l-proline (30 mol %) to give 2-hydroxy-4-oxo-2-substituted pentanenitriles. Upon the treatment with sodium hydroxide, the adducts transformed to 1,3-diketones in good-to-excellent yield, furnishing an efficient and convenient method for the regioselective synthesis of 1,3-diketones.     

Direct addition of supercritical alcohols, acetone or acetonitrile to the alkenes without catalysts

The reactions of the alkenes with supercritical organic compounds under non-catalytic conditions were investigated. The H and CR₂OH, CH₂COCH₃ or CH₂CN of supercritical alcohols (CHR₂OH), acetone (CH₃COCH₃) or acetonitrile (CH₃CN) added to the CC bonds of alkenes form C-C bonds between the α-carbons of the supercritical organic compounds and the sp² carbons of the alkenes.     

Direct synthesis of pyran-lactones related to naphthoquinoneantibiotics

Simple benzopyrans with a fused γ-lactone unit are prepared from an o-disubstituted arene by direct intramolecular alkoxycarbonylation/lactonization promoted by palladium diacetate; the process gives high yields and moderate stereoselectivity, favoring the $\text{cis}$ lactone over $\text{trans}$ by a factor of 5:1.     

Organosilanes in synthesis: application to an enantioselective synthesis of methyl-l-callipeltose

[reaction: see text] Methyl-l-callipeltose, the carbohydrate associated with callipeltoside A, has been synthesized in eight steps and 23% overall yield from enantioenriched allylsilane 6 and acetaldehyde. The key steps are a highly diastereoselective formal [4 + 2] annulation and a Cr(VI)-catalyzed oxidative C-C bond cleavage to produce lactone 11.     

Direct asymmetric aldol reactions of acetone using bimetallic zinc catalysts

[reaction: see text] The enantioselective aldol reaction using a novel binuclear zinc catalyst of acetone with several aldehydes gave products in good yields (62-89%) with a high level of enantioselectivity (ee = 76-92%).     

Facile synthesis of Pd-decorated ZnO nanoparticles for acetone sensors with enhanced performance

ZnO and Pd nanoparticles (NPs) with average diameter of 38 and 10 nm were prepared in advance through a chemical solution method. Pd-functionalized ZnO nanoparticles (Pd@ZnO) were simply synthesized by adding ethanol solution of Pd NPs into ZnO powder, and annealing in argon atmosphere at 500 °C for 1 h after grinding for 30 min. The morphology and structure of the materials were systemically analyzed using Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM) techniques. A weak peak in the XRD pattern of Pd@ZnO belonging to the (111) plane of elemental Pd indicated successfully loading of Pd. EDS and TEM results further confirmed successfully coating of Pd NPs onto the surface of ZnO. Sensors using ZnO NPs decorated with Pd (1 wt%) on the surface of exhibited highly elevated sensitivity of 76 in comparing with the response of 36 when based on pure ZnO NPs. In addition, such modification also resulted in a decrease in the operating temperature from 370 to 340 °C for 100 ppm acetone vapor. The sensing mechanism of the sensor based on Pd@ZnO NPs is discussed. Addition of Pd NPs can play an important role in improving the performance of gas sensors, including high sensitivity, good selectivity, and short response/recovery times.     

Thermal-spectroscopic characterization of acetone peroxide and acetone peroxide mixtures with nitrocompounds

Triacetone triperoxide (TATP), also known as acetone peroxide, is a powerful homemade energetic compound, highly unstable and not detectable by traditional detection technologies. The calorimetric profiles of TATP mixtures with TNT, ammonium nitrate, and nitroguanidine were evaluated and compared to pure materials. Raman spectroscopy was used to identify possible interactions between mixture components that may arise on contact. Typical results show a shift of the TATP decomposition temperature to higher temperatures, as well as decomposition of the nitrocompound initiated by TATP decomposition. The vibrational spectra were used as spectroscopic signatures for these mixtures, which can be used to understand detection challenges and for the development of desensitization approaches.     

Direct glycosylation: synthesis of alpha-indoline ribonucleosides

A selective synthesis of α-anomers of indoline nucleosides is described. Ribonucleosides of indoline, dimethylindoline and 5-bromoindoline are readily prepared in good yield by reacting indoline bases directly with the protected sugar, 2,3-O-(1-methylethylidene) 5-O-(triphenylmethyl)-D-ribofuranose in dry ethanol or methylene chloride in presence of molecular sieves at 40-60 °C.