Highly Selective Construction of Medium-Sized Lactams by Palladium-Catalyzed Intramolecular Hydroaminocarbonylation of Aminoalkynes

A novel palladium-catalyzed intramolecular
hydroaminocarbonylation
of aminoalkynes has been developed. This direct and operationally
simple protocol provides a rapid and reliable approach to a diverse
array of valuable seven- and eight-membered lactams with high chemoselectivity
and regioselectivity. The high selectivity might be attributed to
rational tuning the electronic nature of the amine moiety and the
palladium catalyst, which enabled this transformation to proceed in
the absence of acidic or any other additives under fairly mild reaction
conditions. This method paves the way for the synthesis of medium-sized
lactams.

本研究开发了一种新型钯催化的氨基炔烃分子内氢胺羰基化反应。该方法直接且操作简便，能够以优异的化学选择性与区域选择性，快速可靠地构建一系列具有应用价值的七元及八元内酰胺(lactam)。其高选择性可归因于对胺基片段与钯催化剂电子性质的合理调控，使得该转化可在温和反应条件下，无需酸性试剂或其他添加剂即可顺利进行。该方法为中等环尺寸内酰胺的合成铺平了道路。