Pis Diez C M, Fernandez J F, Di Venosa G, Casas A, Pis Diez R, Palermo J A
Universidad de Buenos Aires, Departamento de Química Orgánica, Facultad de Ciencias Exactas y Naturales, Ciudad Universitaria Pabellón 2 - (1428) Buenos Aires Argentina
CONICET-Universidad de Buenos Aires, Unidad de Microanálisis y Métodos Físicos en Química Orgánica (UMYMFOR) Buenos Aires Argentina.
RSC Adv. 2018 Oct 23;8(63):35998-36006. doi: 10.1039/c8ra05208e. eCollection 2018 Oct 22.
A series of novel 1-(-indolyl)-1,3-butadienes, as (1 : 1) mixtures of the () and () dienes, was prepared in one step by base-catalysed isomerization of -alkylindoles with a terminal butyne chain. The reaction conditions are mild, and in all cases the yields were very high (>90%). The () and () dienes were separable by preparative TLC and could be fully characterized. This isomerization proceeded readily in the case of a butynyl chain, but didn't take place with a pentynyl chain. A mechanism was proposed for this reaction, based on previous studies on the isomerization of alkynes in basic media, and a key intermediate that supports the proposed mechanism could be isolated and fully characterized. A theoretical study of the proposed mechanism was performed by computational methods and the results validated the proposal. The reactivity of the synthesized dienes was studied in Diels-Alder reactions with -benzoquinone, to obtain a small library of new 5-(-indolyl)-1,4-naphthoquinones.The lack of reactivity in the case of the () isomers was explained by calculation of the rotational curves of the central bond of the () and () dienes. Finally, the cytotoxicity of the new 5-(-indolyl)-1,4-naphthoquinones was tested against a panel of three cell lines.
通过碱催化带有末端丁炔链的α-烷基吲哚异构化，一步制备了一系列新型的1-（-吲哚基）-1,3-丁二烯，它们是（）和（）二烯的（1∶1）混合物。反应条件温和，所有情况下产率都非常高（>90%）。（）和（）二烯可通过制备型薄层色谱分离，并能得到充分表征。这种异构化在丁炔链的情况下很容易进行，但在戊炔链的情况下则不会发生。基于先前在碱性介质中炔烃异构化的研究，提出了该反应的机理，并且可以分离并充分表征支持该机理的关键中间体。通过计算方法对提出的机理进行了理论研究，结果验证了该提议。研究了合成二烯与α-苯醌在狄尔斯-阿尔德反应中的反应活性，以获得一个新的5-（-吲哚基）-1,4-萘醌的小型文库。通过计算（）和（）二烯中心键的旋转曲线，解释了（）异构体缺乏反应活性的原因。最后，测试了新的５-（-吲哚基）-1,4-萘醌对一组三种细胞系的细胞毒性。
