Efficient Copper-Catalyzed Multicomponent Synthesis of N-Acyl Amidines via Acyl Nitrenes
| Autor: | Jarl Ivar van der Vlugt, Maxime A. Siegler, Lara H. Polak, Bas de Bruin, Célia Fonseca Guerra, Kaj M. van Vliet |
|---|---|
| Přispěvatelé: | Theoretical Chemistry, AIMMS, Homogeneous and Supramolecular Catalysis (HIMS, FNWI), Institute of Interdisciplinary Studies |
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
chemistry.chemical_classification
Chemistry Xantphos Acetylide Nitrene Aryl Iodide General Chemistry 010402 general chemistry 01 natural sciences Biochemistry Combinatorial chemistry Catalysis Article 0104 chemical sciences Amidine chemistry.chemical_compound Colloid and Surface Chemistry SDG 6 - Clean Water and Sanitation Curtius rearrangement |
| Zdroj: | van Vliet, K M, Polak, L H, Siegler, M A, van der Vlugt, J I, Guerra, C F & de Bruin, B 2019, ' Efficient Copper-Catalyzed Multicomponent Synthesis of N-Acyl Amidines via Acyl Nitrenes ', Journal of the American Chemical Society, vol. 141, no. 38, pp. 15240-15249 . https://doi.org/10.1021/jacs.9b07140 Journal of the American Chemical Society Journal of the American Chemical Society, 141(38), 15240-15249. American Chemical Society |
| ISSN: | 0002-7863 |
| Popis: | Direct synthetic routes to amidines are desired, as they are widely present in many biologically active compounds and organometallic complexes. N-Acyl amidines in particular can be used as a starting material for the synthesis of heterocycles and have several other applications. Here, we describe a fast and practical copper-catalyzed three-component reaction of aryl acetylenes, amines, and easily accessible 1,4,2-dioxazol-5-ones to N-acyl amidines, generating CO2 as the only byproduct. Transformation of the dioxazolones on the Cu catalyst generates acyl nitrenes that rapidly insert into the copper acetylide Cu-C bond rather than undergoing an undesired Curtius rearrangement. For nonaromatic dioxazolones, [Cu(OAc)(Xantphos)] is a superior catalyst for this transformation, leading to full substrate conversion within 10 min. For the direct synthesis of N-benzoyl amidine derivatives from aromatic dioxazolones, [Cu(OAc)(Xantphos)] proved to be inactive, but moderate to good yields were obtained when using simple copper(I) iodide (CuI) as the catalyst. Mechanistic studies revealed the aerobic instability of one of the intermediates at low catalyst loadings, but the reaction could still be performed in air for most substrates when using catalyst loadings of 5 mol The herein reported procedure not only provides a new, practical, and direct route to N-acyl amidines but also represents a new type of C-N bond formation. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|