Simple Synthetic Approach to N -(Pyridin-2-yl)imidates from Nitrostyrenes and 2-Aminopyridines via the N -(Pyridin-2-yl)iminonitriles as Intermediates

• Published in: Molecules (Basel, Switzerland) Vol. 28; no. 8; p. 3321
• Main Authors: Chaidali, Andriani G, Lykakis, Ioannis N
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 09.04.2023; MDPI
• Subjects: 2-aminopyridine; Aluminum oxide; Catalysis; Ethylenediamine; imidates; Imidazole; iminonitriles; Intermediates; Lewis acid; N-heterocycles; nitrostyrenes; Room temperature; Solvents; Substitutes; iminonitriles; nitrostyrenes; 2-aminopyridine; N-heterocycles; imidates
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules28083321

A facile, green, synthetic protocol of several substituted -(pyridin-2-yl)imidates from nitrostyrenes and 2-aminopyridines via the corresponding -(pyridin-2-yl)iminonitriles as intermediates is reported. The reaction process involved the in situ formation of the corresponding α-iminontriles under heterogeneous Lewis acid catalysis in the presence of Al O . Subsequently, α-iminonitriles were selectively transformed into the desired -(pyridin-2-yl)imidates under ambient conditions and in the presence of Cs CO in alcoholic media. Under these conditions, 1,2- and 1,3-propanediols also led to the corresponding mono-substituted imidates at room temperature. The present synthetic protocol was also developed on one mmol scale, providing access to this important scaffold. A preliminary synthetic application of the present -(pyridin-2-yl)imidates was carried out for their facile conversion into the -heterocycles 2-(4-chlorophenyl)-4,5-dihydro-1 -imidazole and 2-(4-chlorophenyl)-1,4,5,6-tetrahydropyrimidine in the presence of the corresponding ethylenediamine and 1,3-diaminopropane.