Abstract:
Reactivity umpolung is an important concept in organic chemistry. Established reactivity umpolung mainly focuses on the aldehyde and umpolung of amide carbonyl group is not known. In this report, we describe a process to obtain the umpolung reactivity of tertiary amide. This process hinges on the efficient reductive stannylation catalyzed by Ir/silane and facile Sn-Li exchange. By leveraging this umpolung reactivity, drug Fluoxetine was derivatized to 12 different analogues via reacting with various electrophiles and four biologically active molecules were prepared concisely. This unlocked umpolung reactivity of tertiary amide is expected to find applications to synthesize complex amines from amides.
摘要:
反应性指数是有机化学中的一个重要概念。建立的反应性增强主要集中在醛上,而酰胺羰基的增强是未知的。在这份报告中,我们描述了获得叔酰胺的umpolung反应性的过程。该过程取决于由Ir/硅烷催化的有效的还原性锡化和容易的Sn-Li交换。通过利用这种不稳定的反应性,通过与各种亲电试剂反应,将药物氟西汀衍生为12种不同的类似物,并简要制备了4种生物活性分子。叔酰胺的这种未锁定的增强反应性有望用于从酰胺合成复合胺。