RESUMEN

We investigate elastic-plastic adhesive wear via a continuum variational phase-field approach. The model seamlessly captures the transition from perfectly brittle, over quasibrittle to elastic-plastic wear regimes, as the ductility of the contacting material increases. Simulation results highlight the existence of a critical condition that morphological features and material ductility need to satisfy for the adhesive junction to detach a wear debris. We propose a new criterion to discriminate between noncritical and critical asperity contacts, where the former produce negligible wear while the latter lead to significant debris formation.

RESUMEN

A direct and efficient regioselective C7-bromination of 4-substituted 1H-indazole has been achieved. Subsequently, a successful palladium-mediated Suzuki-Miyaura reaction of C7-bromo-4-substituted-1H-indazoles with boronic acids has been performed under optimized reaction conditions. A series of new C7 arylated 4-substituted 1H-indazoles was obtained in moderate to good yields.

RESUMEN

In this paper, a new access to several chiral 3-aminoglycals as potential precursors for glycosylated natural products is reported from a common starting material, (-)-methyl-L-lactate. The stereodivergent strategy is based on the implementation of a ring-closing metathesis of vinyl ethers as key step of reaction sequences developed.

RESUMEN

A stereospecific Mizoroki-Heck cross-coupling of differently substituted glycals with haloarenes resulting in the exclusive formation of either α- or ß-aryl-C-glycosides depending solely on the configuration at C3 was achieved. The reaction was easy to set up because no specific precautions were required concerning moisture or oxygen, and it proceeded by a chirality transfer from C3 to C1. After optimization of cross-coupling conditions, various prepared glycals (7 examples) and arenes (10 examples) were tested, leading stereospecifically to the corresponding aryl-C-glycosides with a carbonyl group at C3, thus opening up new horizons for the total synthesis of glycosylated natural products.

RESUMEN

An efficient access for the synthesis of pluramycinones is described. Total syntheses of racemic γ-indomycinone and kidamycinone were achieved by means of two Diels-Alder reactions. A first Diels-Alder condensation followed by a Stille cross-coupling is used for the elaboration of the desired substituted dienes which will be involved in the second pericyclic reaction with juglone to construct the tetracyclic core of pluramycinones.

Asunto(s)

Aneurisma de la Aorta Abdominal/fisiopatología , Disección Aórtica/fisiopatología , Disección Aórtica/etiología , Aorta Abdominal/fisiopatología , Aneurisma de la Aorta Abdominal/etiología , Cateterismo Cardíaco/efectos adversos , Angiografía Coronaria , Electrocardiografía , Femenino , Humanos , Enfermedad Iatrogénica , Persona de Mediana Edad , Remisión Espontánea , Tomografía Computarizada por Rayos X

RESUMEN

A convergent synthesis of the naturally occurring alkaloid Calothrixin B is presented, which used a regioselective hetero-Diels-Alder reaction between a "push-pull" 2-aza-diene and a N-protected 3-bromo-9H-carbazole-1,4-dione to construct the five-ring skeleton of the molecule. Protection of the indole motif with a benzyl group was unattractive for delivery of sufficient target material because the removal of the protecting group had not been high yielding. We therefore elected to temporarily protect the indole motif with a more labile benzyloxycarbonyl group. Accordingly, the synthesis of calothrixin B proceeded in 17% overall yield over 9 steps from the commercially available 1,2,3,9-tetrahydro-4H-carbazol-4-one.

Asunto(s)

Carbazoles/química , Alcaloides Indólicos/síntesis química , Antimaláricos/síntesis química , Antimaláricos/química , Antineoplásicos/síntesis química , Antineoplásicos/química , Ciclización , Alcaloides Indólicos/química , Estructura Molecular , Oxidación-Reducción

RESUMEN

Enantiopure helical poly(quinoxaline-2,3-diyl) was formed stereoselectively in the polymerization of 1,2-diisocyanobenzene using a new organopalladium initiator bearing the (4S,5S)-N-acyl-4,5-dihydro-4,5-diphenyl-1H-imidazol-2-yl group as the polymer-end screw-sense-determinant.