Departamento de Química Orgánica I, Universidad del, País Vasco (UPV/EHU) and Donostia International Physics Center (DIPC), P. K. 1072, 20080 San Sebastián, Spain
Dr. Iván Rivilla
Departamento de Química Orgánica I, Universidad del, País Vasco (UPV/EHU) and Donostia International Physics Center (DIPC), P. K. 1072, 20080 San Sebastián, Spain
The direct functionalization of aromatic C–H bonds by carbene insertion from diazo compounds catalyzed by gold complexes with N-heterocyclic ligands is described. The reaction is completely selective toward the Csp2–H bonds, other Csp3–H bonds remaining unreacted. A study with several NHC ligands in Au(I) and Au(III) complexes has been performed. The potential application of this strategy to give profen derivatives has also been explored.
22 March 2017 in Journal of the American Chemical Society
The importance of systematic and efficient recycling of all forms of plastic is no longer a matter for debate. Constituting the sixth most produced polymer family worldwide, polyurethanes, which are used in a broad variety of applications (buildings, electronics, adhesives, sealants, etc.), are particularly important to recycle. In this study, polyurethanes are selectively recycled to obtain high value-added molecules. It is demonstrated that depolymerization reactions performed with secondary amines selectively cleave the C-O bond of the urethane group, while primary amines unselectively break C-O and C-N bonds. The selective cleavage of C-O bonds, catalyzed by an acid:base mixture, led to the initial polyol and a functional diurea in several hours to a few minutes for both model polyurethanes and commercial polyurethane foams. Different secondary amines were employed as nucleophiles to synthesize a small library of diureas obtained in good to excellent yields. This study not only targets the recovery of the initial polyol but also aims to form new diureas which are useful building blocks for the polymerization of innovative materials.
In the present work, the optimization of the extraction of antioxidant compounds from apple pomace using ultrasound technology as an environmentally friendly and intensification process was developed. Different sonication powers, extraction temperatures and extraction times were studied and their influence on extraction yield and characteristics of the extracted samples (total phenolic compounds, flavonoid content and antioxidant capacity) are presented. The elaborated experimental design and the analysis of Pareto and response surface diagrams allowed us to determine the optimal extraction conditions. The conditions that allow the maximum extraction of phenolic compounds were found at 20 min, 90 °C and 50% ultrasound amplitude. Nevertheless, at these conditions, the antioxidant capacity measured by DPPH decreased in the extracted samples.
We examined the ability of TpxM (Tpx = hydrotris(pyrazolyl)borate ligand; M = Cu and Ag) and IPrMCl (IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene; M = Cu, Ag, Au) complexes as catalyst precursors for the cross-coupling of diazo compounds. Experimental data showed that the metal centre can be tuned with the appropriate selection of the ligand to yield either the homo- or hetero-coupling (cross-coupling) products. A computational study of the reaction mechanism allowed the rationalization of the experimental reactivity patterns, and the identification of the key reaction step controlling the selectivity: the initial reaction between the metallocarbene intermediate and one of the diazo compounds.