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.

Total synthesis of entecavir.

Entecavir (BMS-200475) was synthesized from 4-trimethylsilyl-3-butyn-2-one and acrolein. The key features of its preparation are: (i) a stereoselective boron-aldol reaction to afford the acyclic carbon skeleton of the methylenecylopentane moiety; (ii) its cyclization by a Cp2TiCl-catalyzed intramolecular radical addition of an epoxide to an alkyne; and (iii) the coupling with a purine derivative by a Mitsunobu reaction.

Quality of life, happiness and satisfaction with life of individuals 75 years old or older cared for by a home health care program / Qualidade de vida, felicidade e satisfação com a vida em anciãos com 75 anos ou mais, atendidos num programa de atenção domiciliária / Calidad de vida, felicidad y satisfacción con la vida en personas ancianas de 75 años atendidas en un programa de atención domiciliaria

This case study identifies the elements that compose the Quality of Life (QofL) of individuals who were 75 years old or older and receive care at home. The study’s sample was composed of individuals 75 years or older cared for by a home health care service in the primary health care unit in Vilafranca del Penedès, Spain (n=26). The variables included: a) socio-demographic data; b) concept of QofL; c) perception of QofL; d) reasons for their perception; d) satisfaction with life and related aspects; and f) feeling of happiness. Face to face interviews were conducted. A total of 76.9 percent of the individuals reported a good perception of QofL and the main reasons related to it were: health, family and social relationships, and the ability to adapt. Role Theory and Disengagement Theory explain the adaptation process of these individuals at this point in life.

Objetivou-se detectar os elementos que participam da qualidade de vida (QV) das pessoas com 75 anos, ou mais que recebem cuidados domiciliários. O desenho foi de estudo de caso. A amostra do estudo foi configurada por pessoas com 75 anos, ou mais, atendidas pelo serviço de Atendimento Domiciliário da Área Básica de Vilafranca del Penedès (n=26). As variáveis foram: a) dados sociodemográficos, b) conceito de QV, c) percepção de QV, d) motivos, e) satisfação com a vida e aspectos relacionados e f) sentimento de felicidade. Aplicou-se a técnica da entrevista frente a frente. Do total, 76,9 por cento apresentou boa percepção de QV e os principais elementos relacionados foram: saúde, relações familiares e sociais e adaptação. A teoria dos papéis e a teoria da desvinculação explicam o processo de adaptação desses indivíduos, nessa etapa da vida.

Se objetivó detectar los elementos que participan en la Calidad de Vida (CV) de las personas mayores de 75 años que reciben cuidados domiciliarios. El diseño fue de un estudio de caso. La muestra del estudio la configuraron las personas con 75 años o más, atendidos por el servicio de Atención Domiciliaria del Área Básica de Vilafranca del Penedès (n=26). Las variables fueron: a) datos socio demográficos, b) concepto de CV; c) percepción de CV, d) motivos; e) satisfacción con la vida y aspectos relacionados; f) sentimiento de felicidad. Se aplicó la técnica de la entrevista cara a cara. El 76,9 por ciento presentó una buena percepción de CV y los principales elementos relacionados fueron la salud, las relaciones familiares y sociales y la adaptación. La teoría de los roles y la teoría de la desvinculación explican el proceso de adaptación de estos individuos en esa etapa de la vida.

Stereodivergent addition of 4-silyloxy-1,2-allenes to aldehydes by hydroboration.

All-ene one! Three out of four stereoisomers of 2-vinyl-1,3-diols can be obtained from a single allene. A simple variation of the reaction conditions modifies the stereochemical outcome of the addition of an allene to an aldehyde via hydroboration. Stereocontrol is dependent upon the order in which the reagents are mixed (leading to E or Z boron species) and the type of aldehyde (aliphatic or aromatic) used.

A novel nucleophilic approach to 1-alkyladenosines. A two-step synthesis of [1-15N]adenosine from inosine.

A novel ANRORC mechanism in the reaction of 1-(2,4-dinitrobenzenesulfonyl)inosines with amines has allowed the preparation of 1-alkyladenosines and [1-15N]adenosines in a straightforward way from inosines.

Computational comparison of microtubule-stabilising agents laulimalide and peloruside with taxol and colchicine.

Microtubule-stabilising agents laulimalide and peloruside have been compared with tubulin-interacting drugs paclitaxel and colchicine by different computational approaches. Docking and QSAR-based programs point to a favourable interaction with the beta tubulin paclitaxel binding site, although an additional, preferred binding site has been found at the alpha subunit of tubulin. All together provides a plausible rationalisation of the singular binding features of these microtubule stabilisers and paves the way for future structural studies.

Highly stereoselective approach to alk-2-yne-1,4-diols by oxazaborolidine-mediated reduction of alk-2-yne-1,4-diones.

We performed the borane-mediated reduction of a series of symmetrical alk-2-yne-1,4-diones (5) in the presence of the oxazaborolidine (R)-6 to afford (R,R)-alk-2-yne-1,4-diols ((R,R)-1) in good yields and high stereoselectivities (up to 99.9% ee). In some cases, the stereochemical purity of 1 was improved by a two-step process: (i) temporary transformation of 1 into its vic-dibromo derivatives 9, which allowed us to remove the minor meso isomer by chromatography, and (ii) regeneration of the enantioenriched diols 1 with SmI2. Reduction of the hexacarbonyldicobalt complexes 8 derived from 5 was also successful.

A direct, efficient method for the preparation of n6-protected 15n-labeled adenosines.

N6-Protected adenosines have been prepared from inosines by activation of the C6 position and Pd-catalyzed coupling with amides. An efficient route to [6-15NH2]-N6-benzoyladenosine and [1-15N,6-15NH2]-N6-benzoyladenosine has been achieved.

A new method for the preparation of modified oligonucleotides.

[reaction-see text] N-Nitrothymidine can be transformed into a phosphoramidite building block suitable for oligonucleotide synthesis using the standard phosphite triester solid-phase approach. The N-nitrothymidine residues remain stable during the elongation cycles and react smoothly with primary amines, furnishing oligonucleotides containing N3-modified thymidines. A number of N3-substituted oligonucleotides have been prepared using this methodology, some of them incorporating aminoalkyl or hydroxyalkyl groups.