Stereoselective preparation of quaternary 2-vinyl sphingosines and ceramides and their effect on basal sphingolipid metabolism.

The dicyclohexylborane-mediated addition of allene 1 to (E)-2-tridecenal affords a quaternary protected 2-amino-2-vinyl-1,3-diol in good yield as a single diastereomer. This compound is readily transformed into the four stereoisomers of the quaternary (E)-2-vinyl analogs of sphingosine. The metabolic fate and the effect of these compounds on the basal sphingolipid metabolism in human A549 lung adenocarcinoma cells has been studied, together with the ceramide analog of the most relevant vinylsphingosine derivative.

A Useful Allene for the Stereoselective Synthesis of Protected Quaternary 2-Amino-2-vinyl-1,3-diols.

Treatment of readily available allene 1 with Cy2BH followed by addition of an aldehyde led to quaternary protected 2-amino-2-vinyl-1,3-diols in high yield and excellent stereochemical purity. The choice of benzoyl as N-protecting group is critical since the observed N- to O-Bz transfer during the process prevents later undesired isomerizations in the adducts and keeps all heteroatoms protected.

Catalytic C-H activation of phenylethylamines or benzylamines and their annulation with allenes.

Tetrahydro-3-benzazepines and tetrahydroisoquinolines are synthesized in one step from allenes and phenylethylamines or benzylamines, respectively. Mechanistically, it is assumed that activation of a C-H bond of an aromatic ring with Pd(II) occurs, directed by the primary amine, leading to the formation of a palladacycle into which an allene then undergoes insertion. The resulting π-allyl intermediate cyclizes to the products by an intramolecular allylic alkylation. The process is particularly useful with 2,3-butadienoates and amines having a quaternary carbon at the α-position.

Preparation of benzolactams by Pd(II)-catalyzed carbonylation of N-unprotected arylethylamines.

An unprecedented NH(2)-directed Pd(II)-catalytic carbonylation of quaternary aromatic α-amino esters to yield 6-membered benzolactams has been developed. The reaction shows a strong bias to 6-membered lactams over 5-membered ones. The steric hindrance around the amino group seems to be pivotal for the success of the process.

[Quality evaluation in public health: the case of an animal shelter]. / Evaluación de la calidad en salud pública: aplicación a un centro de acogida de animales de compañía.

OBJECTIVE: There is growing interest in integrating quality approaches to the management of public services. The aim of the present study was to develop a comprehensive evaluation of service quality in the animal shelter managed by the public health services of the city of Barcelona (Catalonia, Spain). METHODS: An evaluation study with three components was performed. Trends in the shelter's activity indicators (2000-2006) were analyzed, compliance with current regulations and protocols was assessed with an internal audit (2006), and user-customer satisfaction was measured with a survey based on the SERVPERF model (2006). RESULTS: The number of animals put to sleep was reduced by almost 70% and the number of adoptions increased. The audit detected 10 non-conformities (3.2% of items), none of which was related to customer service. In the satisfaction survey, the quality dimensions with the highest scores were safety (94.2%) and empathy (81.8%). The emergence of behavioral problems (p=0.039) or health problems (p=0.068) in the adopted animals had a negative influence on quality perception among adopters. CONCLUSIONS: A comprehensive scheme for the evaluation of this service is feasible. There is compliance with established protocols and regulations. The results of the survey show a high degree of user satisfaction.