Synthesis of Functionalized Tetrasubstituted Allenes by the Addition of Bis(trimethylsilyl)ketene Acetals to Ynones Catalyzed by Gold(I).

We have developed a straightforward and rapid methodology for the synthesis of tetrasubstituted allenes bearing carboxylic acids in the 1,3-position through the gold(I)-catalyzed nucleophilic addition of bis(trimethylsilyl)ketene acetals to ynones. The reaction was evaluated with several substrates, and 21 allenes were obtained in moderate to good yields. Using DFT calculations, we studied the mechanism of the reaction, which suggested a nucleophilic 1,4-addition pathway. The potential of allenes to act as a source of highly functionalized lactones was also explored.

Synthesis, Cytotoxic Activity and In Silico Study of Novel Dihydropyridine Carboxylic Acids Derivatives.

To aid the possible prevention of multidrug resistance in tumors and cause lower toxicity, a set of sixteen novel dihydropyridine carboxylic acids derivatives 3a-p were produced; thus, the activation of various ynones with triflic anhydride was performed, involving a nucleophilic addition of several bis(trimethylsilyl) ketene acetals, achieving good yields requiring easy workup. The target molecules were unequivocally characterized by common spectroscopic methods. In addition, two of the tested compounds (3a, and 3b) were selected to perform in silico studies due to the highest cytotoxic activity towards the HCT-15 cell line (7.94 ± 1.6 µM and 9.24 ± 0.9 µM, respectively). Employing theoretical calculations with density functional theory (DFT) using the B3LYP/6-311++G(d,p) showed that the molecular parameters correlate adequately with the experimental results. In contrast, predictions employing Osiris Property Explorer showed that compounds 3a and 3b present physicochemical characteristics that would likely make it an orally active drug. Moreover, the performance of Docking studies with proteins related to the apoptosis pathway allowed a proposal of which compounds could interact with PARP-1 protein. Pondering the obtained results (synthesis, in silico, and cytotoxic activity) of the target compounds, they can be judged as suitable antineoplastic agent candidates.

Synthesis, Molecular Docking, and Antimycotic Evaluation of Some 3-Acyl Imidazo[1,2-a]pyrimidines.

A series of 3-benzoyl imidazo[1,2-a]pyrimidines, obtained from N-heteroarylformamidines in good yields, was tested in silico and in vitro for binding and inhibition of seven Candida species (Candida albicans (ATCC 10231), Candida dubliniensis (CD36), Candida glabrata (CBS138), Candida guilliermondii (ATCC 6260), Candida kefyr, Candida krusei (ATCC 6358) and Candida tropicalis (MYA-3404)). To predict binding mode and energy, each compound was docked in the active site of the lanosterol 14α-demethylase enzyme (CYP51), essential for fungal growth of Candida species. Antimycotic activity was evaluated as the 50% minimum inhibitory concentration (MIC50) for the test compounds and two reference drugs, ketoconazole and fluconazole. All test compounds had a better binding energy (range: -6.11 to -9.43 kcal/mol) than that found for the reference drugs (range: 48.93 to -6.16 kcal/mol). In general, the test compounds showed greater inhibitory activity of yeast growth than the reference drugs. Compounds 4j and 4f were the most active, indicating an important role in biological activity for the benzene ring with electron-withdrawing substituents. These compounds show the best MIC50 against C. guilliermondii and C. glabrata, respectively. The current findings suggest that the 3-benzoyl imidazo[1,2-a]pyrimidine derivatives, herein synthesized by an accessible methodology, are potential antifungal drugs.

Stereodivergent Mannich reaction of bis(trimethylsilyl)ketene acetals with N-tert-butanesulfinyl imines by Lewis acid or Lewis base activation, a one-pot protocol to obtain chiral ß-amino acids.

We report a one-pot synthesis of chiral ß2,2,3-amino acids by the Mannich addition of bistrimethylsilyl ketene acetals to N-tert-butanesulfinyl imines followed by the removal of the chiral auxiliary. The synthesis and isolation of pure ß-amino acid hydrochlorides were conducted under mild conditions, without strong bases and this method is operationally simple. The stereoselective reaction was promoted by two different activation methods that lead to different stereoisomers: (1) Lewis Acid (LA) catalysis with boron trifluoride diethyl etherate and (2) Lewis Base (LB) catalysis with tetrabutylammonium difluorotriphenylsilicate. The reaction presented good diastereoselectivity with LB activation and moderate to good dr with LA catalysis. The exceptions in both protocols were imines with electron donating groups in the aromatic ring.

Innovative Application of Salophen Derivatives in Organic Electronics as a Composite Film with a Poly(3,4-Ethylenedioxythiophene)-poly(styrenesulfonate) Matrix.

In this work, we present the innovative synthesis of salophen (acetaminosalol) derivatives in a solvent-free environment by high-speed ball milling, using a non-conventional activation method, which allowed obtaining compounds in a shorter time and with a better yield. Furthermore, for the first time, the salophen derivatives were deposited as composite films, using a matrix of poly 3,4-ethylene dioxythiophene:polystyrene sulfonate (PEDOT:PSS) polymer. Significant findings include the transformation from the benzoid to the quinoid form of PEDOT post-IPA treatment, as evidenced by Raman spectroscopy. SEM analysis revealed the formation of homogeneous films, and AFM provided insights into the changes in surface roughness and morphology post-IPA treatment, which may be crucial for understanding potential applications in electronics. The optical bandgap ranges between 2.86 and 3.2 eV for PEDOT:PSS-salophen films, placing them as organic semiconductors. The electrical behavior of the PEDOT:PSS-salophen films undergoes a transformation with the increase in voltage, from ohmic to space charge-limited conduction, and subsequently to constant current, with a maximum of 20 mA. These results suggest the possible use of composite films in organic electronics.

Synthesis of New Ruthenium Complexes and Their Exploratory Study as Polymer Hybrid Composites in Organic Electronics.

Polymeric hybrid films, for their application in organic electronics, were produced from new ruthenium indanones in poly(methyl methacrylate) (PMMA) by the drop-casting procedure. Initially, the synthesis and structural characterization of the ruthenium complexes were performed, and subsequently, their properties as a potential semiconductor material were explored. Hence hybrid films in ruthenium complexes were deposited using PMMA as a polymeric matrix. The hybrid films were characterized by infrared spectrophotometry and atomic force microscopy. The obtained results confirmed that the presence of the ruthenium complexes enhanced the mechanical properties in addition to increasing the transmittance, favoring the determination of their optical parameters. Both hybrid films exhibited a maximum stress around 10.5 MPa and a Knoop hardness between 2.1 and 18.4. Regarding the optical parameters, the maximum transparency was obtained at wavelengths greater than 590 nm, the optical band gap was in the range of 1.73-2.24 eV, while the Tauc band gap was in the range of 1.68-2.17 eV, and the Urbach energy was between 0.29 and 0.50 eV. Consequently, the above comments are indicative of an adequate semiconductor behavior; hence, the target polymeric hybrid films must be welcomed as convenient candidates as active layers or transparent electrodes in organic electronics.

Structural determination, characterization and computational studies of doped semiconductors base silicon phthalocyanine dihydroxide and dienynoic acids.

The chemical doping of silicon phthalocyanine dihydroxide (SiPc(OH)2), with (2E, 4Z)-5, 7-diphenylhepta-2, 4-dien-6-ynoic acids (DAc) with electron-withdrawing (BrDAc) and electron-donating (MeODAc) substituents is the main purpose of this work. Theoretical calculations were carried out on Gaussian16 software, with geometrical optimization of all involved species, and obtention of the highest occupied molecule orbital (HOMO), lowest unoccupied molecular orbital (LUMO), and the respective energy gaps. The theoretical calculations show two hydrogen bridge formations: the first one as a peripheral interaction between the terminal oxygen atoms from the acid unit and hydrogen atoms from the phthalocyanine aromatic rings. The second one as the interaction at the nitrogen atoms of the phthalocyanine, which are compelled to form a new flat plane far from the original flat phthalocyanine deck. These organic semiconductors were deposited as thin films and characterized by IR spectroscopy, atomic force microscopy (AFM), and the optical parameters were gathered from UV-Vis studies. The indirect and direct optical band gap, the onset gap and the Urbach energy were obtained. In order to compare the effect of the acids as dopants of the silicon phthalocyanine, the SiPc(OH)2-DAc films were electrically characterized. The SiPc(OH)2-DAc films exhibit an ambipolar electrical behavior, which is influenced by the incidence of different lighting conditions at voltages above 0.3V. The glass/ITO/SiPc(OH)2-MeODAc/Ag reaches a maximum current of 5.68 × 10-5 A for natural light condition, while the glass/ITO/SiPc(OH)2-BrDAc/Ag, reaches a maximum current of 9.21 × 10-9 A for white illumination condition.

New Development of Membrane Base Optoelectronic Devices.

It is known that one factor that affects the operation of optoelectronic devices is the effective protection of the semiconductor materials against environmental conditions. The permeation of atmospheric oxygen and water molecules into the device structure induces degradation of the electrodes and the semiconductor. As a result, in this communication we report the fabrication of semiconductor membranes consisting of Magnesium Phthalocyanine-allene (MgPc-allene) particles dispersed in Nylon 11 films. These membranes combine polymer properties with organic semiconductors properties and also provide a barrier effect for the atmospheric gas molecules. They were prepared by high vacuum evaporation and followed by thermal relaxation technique. For the characterization of the obtained membranes, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS) were used to determine the chemical and microstructural properties. UV-ViS, null ellipsometry, and visible photoluminescence (PL) at room temperature were used to characterize the optoelectronic properties. These results were compared with those obtained for the organic semiconductors: MgPc-allene thin films. Additionally, semiconductor membranes devices have been prepared, and a study of the device electronic transport properties was conducted by measuring electrical current density-voltage (J-V) characteristics by four point probes with different wavelengths. The resistance properties against different environmental molecules are enhanced, maintaining their semiconductor functionality that makes them candidates for optoelectronic applications.