Recently, Tu Shujiang, Hao Wenjuan and Jiang Bo from School of Chemistry and Materials Science led their research team to cooperate with Lanyu and his research group from Zhengzhou University. They made new progress in Azoarene activation for Schmidt-type reaction and the research result was published in Nature Communication with Jiangsu Normal University (JSNU) as the first signature unit. A master student of JSNU, Meng Fantao, and Wang Yanan from Zhengzhou University were the first authors of the paper. Hao Wenjuan, Jiang Bo and Lan Yu were the correspondent authors. The research was supported by the Analysis and Testing Center of Jiangsu Normal University, and was funded by the National Natural Science Foundation of China and the Jiangsu Normal University Natural Science High-quality Scientific Research Excellence Training Project.
“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.”
https://www.nature.com/articles/s41467-022-35141-4