Sequential alcohol oxidation/putative homo Claisen-Tishchenko-type reaction to give esters: a key process in accessing novel biologically active lactone macrocycles

We report an efficient methodology for the direct oxidative esterification of primary alcohols to diether-esters using pyridinium chlorochromate (PCC). Numerous studies were carried out to probe the reaction mechanism and at the same time optimize the reaction conditions. The reaction could be conducted with 1 equivalent of PCC and 1 equivalent of BF3 center dot OEt2. Indications based on literature precedent were that the reaction may proceed via a sequential alcohol oxidation to the aldehyde followed by a putative Cr or boron catalyzed Claisen-Tishchenko-type reaction. Using this efficient methodology, we synthesized a family of novel diether-esters in very good yields; some of these molecules were subsequently tested against both acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE). In addition, we also disclose a new synthetic strategy for the synthesis of lactam macrocycles with potential biological activity. This methodology included the regioselective borylation of the ester substrate and a subsequent Suzuki-Miyaura coupling to obtain the desired lactam macrocycle.

Caos e fractais na sala de aula

O objectivo deste trabalho é o estudo do tema Caos e Fractais, com o propósito fundamental da sua implementação na sala de aula ou outro ambiente do Ensino Secundário. Com esse fim, é feita uma abordagem teórica dos conteúdos e são apresentadas algumas actividades a desenvolver com os alunos daquele nível de ensino. A introdução dos conceitos é feita de modo a possibilitar a sua leitura por um público mais geral, onde se incluem os alunos mais interessados e curiosos no tema. O estudo é acompanhado, sempre que possível, de exemplos e ilustrações gráficas. Para tal, foi utilizado o software Maxima (software livre) e outras aplicações interactivas disponíveis na Internet. ABSTRACT: The aim of this work is to study the theme of Chaos and Fractals, with the fundamental purpose of its implementation in the classroom, or in other environments of secondary school education. To carry out this aim a theoretical outlook of the contents will be provided alongside some activities to be undergone with students of that school level. The introduction to these concepts is open to the understanding of a larger audience, where we can include the most interested and curious students in this issue. The study is accompanied, whenever possible, with examples and graphics. To do so, the Maxima software (free software) was used, besides other interactive applications available on the Internet.