IGLESIAS SIGÜENZA , Francisco Javier

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La presente Tesis Doctoral ha sido diseñada y ejecutada con el objetivo fundamental de desarrollar aplicaciones de interés en el campo de la catálisis enantioselectiva. En concreto, se han desarrollado nuevas familias de carbenos N-heterocíclicos estables, h aciendo especial énfasis en el estudio de la posibilidad de introducción de quiralidad...

En esta comunicación se presentan una estrategia de mejora docente progresiva basada en los denominados Ciclos de Mejora Docente, los cuales se han realizado en una parte del temario de la asignatura "Química General" del Grado en Química. Estos ciclos de mejora contemplan una reflexión sobre el modelo metodológico empleado, los contenidos...

El objetivo del trabajo es analizar la eficacia de la metodología del aprendizaje basado en problemas (ABP) en una titulación del grupo de las STEM, en concreto en tres asignaturas de 1º, 2º y 3º del Grado en Química de la Universidad de Sevilla. Las clases se convierten para los estudiantes en un lugar de trabajo en grupo en el que deben...

The direct dialkylation of triazolo[4,3-b]isoquinolin-3-ylidene structures readily affords dicationic N-heterotricyclic azolium salts. These are suitable starting materials for the synthesis of transition metal complexes containing N-heterotricyclic, cationic ligands characterized by extended charge delocalization. Silver and gold complexes as...

The benzoannulation of the most common families of aromatic NHCs, imidazol-2-ylidenes and 1,2,4-triazol-3-ylidenes, results in heterobicyclic imidazo[1,5-a]pyridin-3-ylidenes (ImPy's) and [1,2,4]triazolo[4,3-a]pyridin-3-ylidenes (TriPy's), characterized by a bridged N atom. These are versatile platforms that offer multiple possibilities for the...

The Pd-catalyzed coupling of racemic heterobiaryl bromides, triflates, or nonaflates with aryl/alkyl primary amines using QUINAP as the ligand provides the corresponding axially chiral heterobiaryl amines with excellent yields and enantioselectivities. Reactivity and structural studies of neutral and cationic oxidative addition intermediates...

A highly enantio- and diastereoselective thiourea-catalyzed dearomatization of isoquinolines employing N-tert-butylhydrazones as neutral α-azo carbanions and masked acyl anion equivalents has been developed. Experimental and computational data supports the generation of highly ordered complexes wherein the chloride behaves as a template for the...

The formal insertion of alkenes into aromatic chloro- and bromoalkynes takes place under cationic gold catalysis. This haloalkynylation reaction can be performed with cyclic, gem-disubstituted and monosubstituted alkenes, using BINAP, triazolo[4,3-b]isoquinolin-3-ylidene ligands or SPhos, respectively. The products were isolated in moderate to...

Complex [PtMe(PMeAr)] (1), which contains a tethered terphenyl phosphine (Ar =2,6-(2,6-PrCH)CH), reacts with [H(EtO)]BAr (BAr =B[3,5-(CF)CH] ) to give the solvent (S) complex [PtMe(S)(PMeAr)] (2⋅S). Although the solvent molecule is easily displaced by a Lewis base (e.g., CO or CH) to afford the corresponding adducts, treatment of 2⋅S with CH...

Catalysts generated by combinations of Pd(TFA)2and pyridine-hydrazone ligands have allowed the asymmetric 1,2-addition of aryl boronic acids toN-carbamoyl (Cbz and Fmoc) protected glyoxylate-derived hydrazones, yielding a-aryl a-hydrazino esters/amides in high enantioselectivities. Subsequent removal of the carbamoyl moiety affords key building...

The nucleophilic addition of formaldehyde tert-butylhydrazone to simple aldehydes (a formal hetero-carbonyl–ene reaction) can be performed with good reactivity and excellent enantioselectivity by virtue of the dual hydrogen-bonding activation exerted by amide–squaramide organocatalysts. The resulting hydroxydiazenes (azo alcohols) were isolated...

A highly regio-, diastereo-, and enantioselective, scalable Ir-catalyzed hydroarylation of electron-rich acyclic and tensioned cyclic olefins with heterobiaryls is described. The reaction of acyclic vinyl ethers, dihydrofuran, and norbornenes with a variety of aryl isoquinoline, quinazoline, and picoline derivatives takes place with...

Adiastereo- and highly enantioselective dynamic kinetic resolution (DKR) of configurationally labile hetero- biaryl ketones is described. The DKR proceeds by zinc- catalyze dhydrosilylation of the carbonyl group ,thus leading to secondary alcohols bearing axial and central chirality .The strategy relies on the labilization of the...

The geometries and coordination properties of modular pyridineehydrazone N,N-ligands containing C2- symmetric trans-2,5-diphenylpyrrolidine and trans-2,5-diphenylpiperidine as the terminal dialkylamino units have been analyzed by X-ray diffraction analysis of [PdCl2(N,N)] complexes [(N,N)¼pyridine hy- drazone ligand]. In combination with...

A dynamic kinetic asymmetric Pd-catalyzed cross-coupling reaction of heterobiaryl bromides with ketone N-tosylhydrazones for the synthesis of heterobiaryl styrenes is described. The combination of Pd(dba)2 as a precatalyst with a TADDOL-derived phosphoramidite ligand provides the corresponding coupling products in good yields and high...

Catalysts generated by combinations of Pd(TFA)2 and pyridine-hydrazone ligands have been applied to 1,2 addition of arylboronic acids to aliphatic N-carbamoyl (Cbz) hydrazones, affording protected α- aryl monoalkylhydrazines with high enantioselectivities (37-99% ee). Subsequent removal of the benzyloxy carbonyl protecting group provides a...

The first highly enantioselective intermolecular (4 + 2) cycloaddition between allenes and dienes is reported. The reaction provides good yields of optically active cyclohexenes featuring diverse substitution patterns and up to three stereocenters. Key to the success of the process is the use of newly designed axially chiral N-heterocyclic...

The AuI-catalyzed reaction between terminal alkynes and aromatic haloalkynes proceeds through divergent pathways depending on the nature of the catalyst counteranion. Thus, cationic complexes containing strongly basic NHC ligands and noncoordinating anions such as BArF4 catalyze the cis haloalkynylation of the terminal alkyne, whereas...

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...

A highly enantioselective biocatalytic dynamic kinetic resolution (DKR) of configurationally labile N-arylindole aldehydes is described. The DKR proceeds by atroposelective bioreduction of the carbonyl group catalyzed by commercial ketoreductases (KREDs), thus affording the corresponding axially chiral N-arylindole aminoalcohols, with excellent...