Affiliation:
1. School of Natural Sciences Macquarie University North Ryde NSW 2109 Australia
2. Institute of Chemical Technology Ural Federal University 19 Mira Str. Yekaterinburg 620002 Russian Federation
3. Molecular Horizons and School of Chemistry and Molecular Bioscience University of Wollongong Wollongong NSW 2522 Australia
Abstract
Abstract1,2,3‐Thiadiazoles exhibit versatile reactivity due to their ability to undergo ring cleavage, forming α‐diazothione species through a Dimroth‐type equilibrium. Denitrogenation of the α‐diazothione, induced by high temperature, irradiation, or strong bases, allows generation of a wide range of reactive intermediates. Since 2016, the transition‐metal‐catalyzed denitrogenative transannulation of 1,2,3‐thiadiazoles has garnered significant attention as a promising approach to constructing diverse heterocyclic scaffolds. This review focuses on the denitrogenative reactions of 1,2,3‐thiadiazoles, particularly highlighting the novel rhodium‐catalyzed denitrogenative transannulation transformations along with their mechanisms.