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Tandem Cycloaddition of Azides to 3,3-Diaminoacrylonitriles (2-Cyanoacetamidines) and Cornforth-Type Rearrangement as an Approach to 5-Amino-1,2,3-triazole-4-N-substituted Imidamides.
Silaichev, Pavel S; Beryozkina, Tetyana V; Ilkin, Vladimir; Novikov, Mikhail S; Dehaen, Wim; Bakulev, Vasiliy A.
Afiliación
  • Silaichev PS; Department of Chemistry, Perm State University, 15 Bukireva st, Perm 614990, Russia.
  • Beryozkina TV; ITMO University, 49 Kronverksky Pr., St. Petersburg 197101, Russia.
  • Ilkin V; Ural Federal University named after the first President of Russia B. N. Yeltsin, 19 Mira st, Yekaterinburg 620002, Russia.
  • Novikov MS; Ural Federal University named after the first President of Russia B. N. Yeltsin, 19 Mira st, Yekaterinburg 620002, Russia.
  • Dehaen W; Institute of Chemistry, St. Petersburg State University, 7/9 Universitetskaya nab, St. Petersburg 199034, Russia.
  • Bakulev VA; Molecular Design and Synthesis, Department of Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium.
J Org Chem ; 88(13): 8163-8174, 2023 Jul 07.
Article en En | MEDLINE | ID: mdl-37347661
An efficient base-catalyzed, metal-free method for the synthesis of 5-amino-1,2,3-triazole-4-N-sulfonyl- and arylimidamides, directed by the structure of the amidine group, has been developed. It is based on a previously unknown tandem process involving cycloaddition reaction to 3,3-diaminoacrylonitriles (2-cyanoacetamidines) with aryl(alkyl)sulfonyl or aryl azides and Cornforth-type rearrangement. During the reaction optimization, different factors were found to facilitate the title reaction, which include the use of a strong base and N-mono- or N,N'-disubstituted 3,3-diaminoacrylonitriles. The reaction is tolerant to variously N-monosubstituted and N,N'-disubstituted 3,3-diaminoacrylonitriles and to various aryl- and aryl/alkyl sulfonyl azides. The developed method has a broad scope and can be applied to obtain a variety of 5-amino-1,2,3-triazole-4-carbimidamides bearing at the N1 position alkyl, allyl, propargyl, benzyl, cycloalkyl, and heteroaryl substituents and sulfonyl and aryl substituents at the amidine group. Post-cyclization reactions of prepared 5-amino-1,2,3-triazoles with DMF-DMA DMA-DMF leads to 1,2,3-triazolo[4,5-d]pyrimidines, 8-aza purine analogues demonstrating the applicability of the prepared compounds in organic synthesis.
Asunto(s)

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Azidas / Triazoles Idioma: En Revista: J Org Chem Año: 2023 Tipo del documento: Article País de afiliación: Rusia Pais de publicación: Estados Unidos

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Azidas / Triazoles Idioma: En Revista: J Org Chem Año: 2023 Tipo del documento: Article País de afiliación: Rusia Pais de publicación: Estados Unidos