IIQ
José A. Carmona, Valentín Hornillos, Pedro Ramírez-López, Abel Ros, Javier Iglesias-Sigüenza, Enrique Gómez-Bengoa, Rosario Fernández, and José M. Lassaletta Journal of the American Chemical Society 2018, Vol. 35, 11067
A highly diastereo- and enantioselective, scalable Pd-catalyzed dynamic kinetic asymmetric Heck reaction of heterobiaryl sulfonates with electron-rich olefins is described. The coupling of 2,3-dihydrofuran or N-boc protected 2,3-dihydropyrrole with a variety of quinoline, quinazoline, phthalazine, and picoline derivatives takes place with simultaneous installation of central and axial chirality, reaching excellent diastereo- and enantiomeric excesses when in situ formed [Pd0/DM-BINAP] was used as the catalyst, with loadings reduced down to 2 mol % in large scale reactions. The coupling of acyclic, electron-rich alkenes can also be performed using a [Pd0/Josiphos ligand] to obtain axially chiral heterobiaryl α-substituted alkenes in high yields and enantioselectivities. Products from Boc-protected 2,3-dihydropyrrole can be easily transformed into N,N ligands or appealing axially chiral, bifunctional proline-type organocatalysts. Computational studies suggest that a β-hydride elimination is the stereocontrolling step, in agreement with the observed stereochemical outcome of the reaction.
Los artículos seleccionados serán destacados como artículos del mes y participarán en el Premio de Investigación cicCartuja-Ebro Foods, que se entregará al final de cada año. Se concederá un premio al ganador dotado con 6.000 euros y dos accésits de 3.000 euros cada uno para los siguientes clasificados.