Recent Advances in the Denitrogenative Annulation Reactions of 1,2,3‐Thiadiazoles

• Published in: ChemCatChem 2024-07, Vol.16 (14), p.n/a
• Main Authors: Tokareva, Marina A., Glukhareva, Tatiana V., Keaveney, Sinead T.
• Format: Article
• Language: English
• Subjects: 1,2,3-thiadiazole; catalysis; Chemical reactions; Denitrogenation; heterocycles; High temperature; Rhodium; Thiadiazoles
• ISSN: 1867-3880; 1867-3899
• DOI: 10.1002/cctc.202301488

1,2,3‐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. The denitrogenative annulation of 1,2,3‐thiadiazoles has emerged as an important strategy in organic synthesis, as it can permit streamlined access to a variety of functionalised heterocyclic compounds from a common, stable building. This review focuses on the denitrogenative reactions of 1,2,3‐thiadiazoles, particularly focused on novel rhodium‐catalyzed methodology.