Azoarene activation for Schmidt-type reaction and mechanistic insights

Fan-Tao Meng, Ya-Nan Wang, Xiao-Yan Qin, Shi-Jun Li, Jing Li, Wen-Juan Hao (), Shu-Jiang Tu, Yu Lan () and Bo Jiang ()
Additional contact information
Fan-Tao Meng: Jiangsu Normal University
Ya-Nan Wang: Zhengzhou University
Xiao-Yan Qin: Jiangsu Normal University
Shi-Jun Li: Zhengzhou University
Jing Li: Jiangsu Normal University
Wen-Juan Hao: Jiangsu Normal University
Shu-Jiang Tu: Jiangsu Normal University
Yu Lan: Zhengzhou University
Bo Jiang: Jiangsu Normal University

Nature Communications, 2022, vol. 13, issue 1, 1-12

Abstract: Abstract 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.

Date: 2022
References: View references in EconPapers View complete reference list from CitEc
Citations:

Downloads: (external link)
https://www.nature.com/articles/s41467-022-35141-4 Abstract (text/html)

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-35141-4

Ordering information: This journal article can be ordered from
https://www.nature.com/ncomms/

DOI: 10.1038/s41467-022-35141-4

Access Statistics for this article

Nature Communications is currently edited by Nathalie Le Bot, Enda Bergin and Fiona Gillespie

More articles in Nature Communications from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().