Metal‐Free Synthesis of Functional 1‐Substituted‐1, 2, 3‐Triazoles from Ethenesulfonyl Fluoride and Organic Azides. (28th November 2019)

• Record Type: Journal Article
• Authors: Giel, Marie‐Claire; Smedley, Christopher J.; Mackie, Emily R. R.; Guo, Taijie; Dong, Jiajia; Soares da Costa, Tatiana P.; Moses, John E.
• Is Part Of: Angewandte Chemie. Volume 132:Number 3(2020)
• Page Start: 1197
• Page End: 1202
• Publication Date: 2019-11-28
• Subjects: Acetylen -- Cycloaddition -- Heterocyclen -- Klick-Chemie -- Synthesemethoden; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201912728
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The boom in growth of 1, 4‐disubstituted triazole products, in particular, since the early 2000's, can be largely attributed to the birth of click chemistry and the discovery of the Cu I ‐catalyzed azide–alkyne cycloaddition (CuAAC). Yet the synthesis of relatively simple, albeit important, 1‐substituted‐1, 2, 3‐triazoles has been surprisingly more challenging. Reported here is a straightforward and scalable click‐inspired protocol for the synthesis of 1‐substituted‐1, 2, 3‐triazoles from organic azides and the bench stable acetylene surrogate ethenesulfonyl fluoride (ESF). The new transformation tolerates a wide selection of substrates and proceeds smoothly under metal‐free conditions to give the products in excellent yield. Under controlled acidic conditions, the 1‐substituted‐1, 2, 3‐triazole products undergo a Michael addition reaction with a second equivalent of ESF to give the unprecedented 1‐substituted triazolium sulfonyl fluoride salts. Abstract : Ein metallfreies Klick‐Protokoll für die Synthese von 1‐substituierten 1, 2, 3‐Triazolen aus organischen Aziden und Ethensulfonylfluorid (ESF) wird beschrieben. Der präparative Nutzen der konzertierten Reaktion zeigt sich in der Ein‐Topf‐Synthese der Triazole im Gramm‐Maßstab und in der Modifizierung mehrerer Wirkstoffe, darunter des Antibiotikums Chloramphenicol, aus dem ein neues aktives Antibiotikum gebildet wurde.