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1.
J Org Chem ; 78(14): 6890-910, 2013 Jul 19.
Artigo em Inglês | MEDLINE | ID: mdl-23641810

RESUMO

In this work, we report on a new intramolecular para cycloaddition of arenes with allenes, yielding attractive rigid scaffolds bearing several reactive functionalities to build in further diversity. Bicyclo[2.2.2]octadiene-type products and benzoxepine acetals are formed in this reaction, in ratios and yields depending on the substitution pattern on the aromatic ring, the nature of the chromophore, and the tether. This unprecedented reaction has remarkable features that distinguish it from many other photochemical transformations: it is particularly robust with respect to substituents, it can be scaled up without a notable loss of efficiency, and it can lead to structures with a high degree of complexity in low to good yields. All photochemical precursors could be synthesized readily in three steps. We confirmed the compatibility of the nitrogen atom in the photocycloaddition step, which gives access to a bicyclo[2.2.2]octadiene scaffold with two points that allow further diversification. This reaction was scaled up to multigram quantities without erosion of the typically high yields in photocycloadducts. Sequential deprotection of the N- or C-terminus of bicyclic amino acids gave access to two conformationally constrained unnatural amino acids with different dispositions of the two anchor points.


Assuntos
Alcadienos/química , Derivados de Benzeno/química , Benzoxepinas/síntese química , Compostos Bicíclicos com Pontes/síntese química , Benzoxepinas/química , Compostos Bicíclicos com Pontes/química , Ciclização , Estrutura Molecular , Processos Fotoquímicos , Estereoisomerismo
2.
Beilstein J Org Chem ; 7: 525-42, 2011.
Artigo em Inglês | MEDLINE | ID: mdl-21647263

RESUMO

In the presence of an alkene, three different modes of photocycloaddition with benzene derivatives can occur; the [2 + 2] or ortho, the [3 + 2] or meta, and the [4 + 2] or para photocycloaddition. This short review aims to demonstrate the synthetic power of these photocycloadditions.

3.
Sante Ment Que ; 33(2): 31-47, 2008.
Artigo em Francês | MEDLINE | ID: mdl-19370256

RESUMO

Interpersonal Psychotherapy was developed in the years 1969-84, specifically at that time, for the treatment of depression (later called Major Depression). Today, its indications have been extended to numerous other clinical syndromes and situations. This article describes the empirical basis on which IPT was developed until it evolved to its current format. A description of the phases of treatment is presented and the four problem areas commonly encountered in IPT are more explicitly detailed. Several techniques utilized in the course of this treatment are enumerated and the strategy underlying their usage is explained. IPT is an evidence-based psychotherapy and a clarification is made about its specificity, compared to other commonly used forms of psychotherapy.


Assuntos
Psicoterapia/métodos , Transtorno Depressivo Maior/terapia , História do Século XX , História do Século XXI , Humanos , Psicoterapia/história
4.
Org Lett ; 19(7): 1538-1541, 2017 04 07.
Artigo em Inglês | MEDLINE | ID: mdl-28350459

RESUMO

Signal transducer and activator of transcription 3 (STAT3) is a component of the JAK/STAT pathway. Therapeutic inhibition of STAT3 has been of high interest, as its aberrant activation has been linked to cancer, inflammation, and other human diseases. The withanolide family natural product withaferin A (1) inhibits STAT3 activation. We designed, synthesized, and evaluated simplified withanolide analogues SLW1 (3) and SLW2 (4), and found that SLW1 retained the STAT3 inhibitory activity of withaferin A.

5.
Sante Ment Que ; 29(1): 173-200, 2004.
Artigo em Francês | MEDLINE | ID: mdl-15470572

RESUMO

For the past decades, in a world of high competition, firms struggle to regain an advantage over foreign competition. Thus, new management trends, usually based on price reduction, high quality products and speed production are now part of strategic reorganization plans of high impact on work organization particularly in terms of large demands put on workers, and take a heavy toll on workers. Thus the incidence of mental health problems in the work place has risen sharply in recent years and currently counts as one of the leading causes of work absenteeism. A study based on the psychodynamic of work was conducted among machine operators working in a high-technology company in the aviation sector. Important management and technological transformations were recently introduced in the factory. The content analysis of the study shows that the work organization places the operator in a double bind situation. They are caught between an injunction where the capacity of making a high quality product is directly opposed to that demanding speed production. Moreover, severe and arbitrary sanctions are applied when the operators do not comply with either injunction. The operators are put in a deadlock situation that creates fear and anxiety. They are obliged to turn to defensive psychological strategies such as individualism and cheating. Those defensive strategies have negative impacts on social relationships.


Assuntos
Transtornos de Ansiedade/diagnóstico , Interação do Duplo Vínculo , Doenças Profissionais/diagnóstico , Objetivos Organizacionais , Estresse Psicológico/complicações , Carga de Trabalho/psicologia , Transtornos de Ansiedade/epidemiologia , Transtornos de Ansiedade/psicologia , Estudos Transversais , Mecanismos de Defesa , Competição Econômica , Eficiência Organizacional/economia , Humanos , Relações Interpessoais , Doenças Profissionais/epidemiologia , Doenças Profissionais/psicologia , Inovação Organizacional/economia , Objetivos Organizacionais/economia , Gestão de Recursos Humanos/economia , Fatores de Risco , Carga de Trabalho/economia
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