The Schmidt rearrangement, a reaction that enables C-C or C-H σ bond cleavage and nitrogen insertion across an aldehyde or ketone substrate, is one of the most important and widely used synthetic tools for the installation of amides and nitriles. However, such a reaction frequently requires volatile, potentially explosive, and highly toxic azide reagents as the nitrogen donor, thus limiting its application to some extent. Here, we show a Schmidt-type reaction where aryldiazonium salts act as the nitrogen precursor and in-situ-generated cyclopenta-1,4-dien-1-yl acetates serve as pronucleophiles from gold-catalyzed Nazarov cyclization of 1,3-enyne acetates. Noteworthy is that cycloketone-derived 1,3-enyne acetates enabled ring-expansion relay to access a series of 2-pyridone-containing fused heterocycles, in which nonsymmetric cycloketone-derived counterparts demonstrated high regioselectivity. Aside from investigating the scope of this Schmidt-type reaction, mechanistic details of this transformation are provided by performing systematic theoretical calculations.

施密特重排是一种能够在醛或酮底物上进行 CC 或 CH σ 键断裂和氮插入的反应，是用于安装酰胺和腈的最重要和广泛使用的合成工具之一。然而，此类反应往往需要使用易挥发、易爆、剧毒的叠氮试剂作为供氮体，从而在一定程度上限制了其应用。在这里，我们展示了一个 Schmidt 型反应，其中芳基重氮盐充当氮前驱体并原位-生成的 cyclopenta-1,4-dien-1-yl acetates 作为金催化的 1,3-enyne acetates 的 Nazarov 环化的亲核试剂。值得注意的是，环酮衍生的 1,3-烯炔乙酸酯使环扩展接力获得一系列含 2-吡啶酮的稠合杂环，其中非对称环酮衍生的对应物表现出高区域选择性。除了研究这种施密特型反应的范围外，还通过系统的理论计​​算提供了这种转变的机理细节。