Alejandro Camacho-Dávila

Kumada–Corriu Cross Coupling Route to the Anti-Cancer Agent Combretastatin A-4

Abstract A short and efficient synthesis of the anticancer agent combretastatin A-4 was accomplished from inexpensive starting materials using the iron-catalyzed cross-coupling of a Grignard reagent and a bromostilbene as the key step.

Experimental and quantum chemical studies of a novel synthetic prenylated chalcone

BackgroundChalcones are ubiquitous natural compounds with a wide variety of reported biological activities, including antitumoral, antiviral and antimicrobial effects. Furthermore, chalcones are being studied for its potential use in organic electroluminescent devices; therefore the description of their spectroscopic properties is important to elucidate the structure of these molecules. One of the main techniques available for structure elucidation is the use of Nuclear Magnetic Resonance Spectroscopy (NMR). Accordingly, the prediction of the NMR spectra in this kind of molecules is necessary to gather information about the influence of substituents on their spectra.ResultsA novel substituted chalcone has been synthetized. In order to identify the functional groups present in the new synthesized compound and confirm its chemical structure, experimental and theoretical 1H-NMR and 13C-NMR spectra were analyzed. The theoretical molecular structure and NMR spectra were calculated at both the Hartree-Fock and Density Functional (meta: TPSS; hybrid: B3LYP and PBE1PBE; hybrid meta GGA: M05-2X and M06-2X) levels of theory in combination with a 6-311++G(d,p) basis set. The structural parameters showed that the best method for geometry optimization was DFT:M06-2X/6-311++G(d,p), whereas the calculated bond angles and bond distances match experimental values of similar chalcone derivatives. The NMR calculations were carried out using the Gauge-Independent Atomic Orbital (GIAO) formalism in a DFT:M06-2X/6-311++G(d,p) optimized geometry.ConclusionConsidering all HF and DFT methods with GIAO calculations, TPSS and PBE1PBE were the most accurate methods used for calculation of 1H-NMR and 13C-NMR chemical shifts, which was almost similar to the B3LYP functional, followed in order by HF, M05-2X and M06-2X methods. All calculations were done using the Gaussian 09 software package. Theoretical calculations can be used to predict and confirm the structure of substituted chalcones with good correlation with the experimental data.

Pyrene-Fullerene C60 Dyads as Light-Harvesting Antennas

A series of pyrene-fullerene C60 dyads bearing pyrene units (PyFC12, PyFPy, Py2FC12 and PyFN) were synthesized and characterized. Their optical properties were studied by absorption and fluorescence spectroscopies. Dyads were designed in this way because the pyrene moeities act as light-harvesting molecules and are able to produce “monomer” (PyFC12) or excimer emission (PyFPy, Py2FC12 and PyFN). The fluorescence spectra of the dyads exhibited a significant decrease in the amount of pyrene monomer and excimer emission, without the appearance of a new emission band due to fullerene C60. The pyrene fluorescence quenching was found to be almost quantitative, ranging between 96%–99% depending on the construct, which is an indication that energy transfer occurred from one of the excited pyrene species to the fullerene C60.

Synthesis, electronic, and spectral properties of novel geranylated chalcone derivatives: a theoretical and experimental study.

AbstractNovel chalcone derivatives with different substituents attached to A and B-rings: hydroxyl, methoxyl, geranyl, and prenyl groups were synthesized. The obtained compounds were characterized by NMR, HRMS, UV-Vis, IR, and MS. The theoretical analysis was carried out in all the compounds using density functional theory (DFT) with the B3LYP, PBE0, and M06-2X functionals in combination with the 6-311G(d,p) Pople-type basis set. The excited state properties were calculated by time dependent density functional theory (TD-DFT) using the same methodology applied for the ground state properties. The calculated vertical absorption wavelengths (λmax) in gas phase and in ethanol as a solvent are consistent with the experimental ones, being the TD-DFT:B3LYP/6-311G(d,p) and PCM-TD-DFT:PBE0/6-311G(d,p) the best methodologies for these calculations with good approximation to the experimental values. The calculated reorganization energies indicated that, the four chalcone derivatives present an electron transfer character due to the smaller registered values. From these parameters it is proposed that these show an n-type semiconductor character. The localization of the frontier orbitals (HOMO and LUMO) shows that only the compound containing a hydroxyl group on the A-ring displays a marked delocalization favoring the charge-transfer process in this system. The HOMO-LUMO gap energies indicate that the inclusion of different donor groups in the rings does not improve the obtained values for this property. Graphical AbstractRelationship between spectroscopic and geometrical properties of chalcones were carried out using quantum-chemical calculations and compared with experimental values.

Synthesis of a Functionalized Benzofuran as a Synthon for Salvianolic Acid C Analogues as Potential LDL Antioxidants

A palladium mediated synthesis of a common synthon for the syntheses of antioxidant analogues of naturally occurring salvianolic acids is presented. The synthetic route may be used to obtain analogues with a balanced lipophilicity/hydrophilicity which may result in potentially interesting LDL antioxidants for the prevention of cardiovascular diseases.

Biopolymers from Waste Biomass — Extraction, Modification and Ulterior Uses

The residues coming from woodlands and agricultural exploitation constitute the most abundant biomass available on earth. Its importance as a source of renewable energy has grown in addition to the environmental impact. Biomass waste is a lignocellulosic feedstock which contains three main biopolymers: cellulose, hemicel‐ lulose and lignin. It could be utilized for the production of a number of value-added products due to their chemical composition, but it is necessary to efficiently recover the valuable biopolymer as intact as possible by different processing techniques.For different applications, the principal objective of pre-treatment is to keep the cellu‐ lose intact, meanwhile hemicellulose and lignin are removed. The yields of the frac‐ tions depend on the pre-treatment method, which is the most expensive step in biomass conversion. Traditionally, cellulose is obtained by kraft, sulphite and soda treatments. These methods are non-environmentally friendly and generate huge quantities of toxic wastes. Recently developed models considering the environmen‐ tal laws encourage the sustainable processing of biomass into value-added prod‐ ucts. The use of ionic liquids as new solvents for biomass waste and organosolv processes is reviewed, which are used to obtain cellulose. One of the possible appli‐ cations of cellulose is membrane synthesis, which has been reported for other bio‐ mass materials, such as sugarcane bagasse, mango seed and newspaper. In this chapter, some green pre-treatment methods, different sustainable routes for cellu‐ lose modification and some of the results obtained on membrane development based on waste biomass are discussed.

Synthesis of exo-Imidazolidin-2-one Dienes, Their Isomerization, and Selectivity in Diels–Alder Cycloadditions

An efficient and alternative synthesis of exo-imidazolidin-2-one dienes is described. A condensation reaction was carried out with bis-imino derivatives, diacetyl, and triphosgene, affording symmetrically N, N-disubstituted dienes. The use of alkyl methyl α-diketones led to the formation of nonsymmetrical dienes, which underwent isomerization to provide more stable inner-outer-ring dienes under Lewis acid conditions. Evaluation was made of the reactivity as well as regio- and stereoselectivity of these dienes in Diels-Alder reactions. They proved to be highly reactive and selective. DFT calculations of the transition states accounted for their behavior.

Lipase catalyzed epoxidation of fatty acid methyl esters derived from unsaturated vegetable oils in absence of carboxylic acid

Nowadays the industrial chemistry reactions rely on green technologies. Enzymes as lipases are increasing its use in diverse chemical processes. Epoxidized fatty acid methyl esters obtained from transesterification of vegetable oils have recently found applications as polymer plasticizer, agrochemical, cosmetics, pharmaceuticals and food additives. In this research article, grapeseed, avocado and olive oils naturally containing high percents of mono and poly unsaturations were used as starting materials for the production of unsaturated fatty acid methyl esters. The effect of lauric acid as an active oxygen carrier was studied on epoxidation reactions where unsaturated fatty acid methyl esters were converted to epoxy fatty acid methyl esters using immobilized Candida antarctica Lipase type B as catalyst and hydrogen peroxide as oxygen donor at mild temperature and pressure conditions. After this study it was confirmed by 1H NMR, 13C NMR and GC–MS that the addition of lauric acid to the enzymatic reaction is unnecessary to transform the alkenes in to epoxides. It was found that quantitative conversions were possible in despite of a carboxylic acid absence.

Sustainable Synthesis of the Naturally Hypolipidemic Agent α-Asarone

Abstract A short and practical preparation of α-asarone was developed using the inexpensive methylisoeugenol as a starting material. The utilization of a sequence of tribromination, debromination, and copper-mediated aromatic substitution enabled the stereoselective formation of only the E-isomer of α-asarone in good yield. GRAPHICAL ABSTRACT