2,6-Dicyano-4-pyrone as a Novel and Multifarious Building Block for the Synthesis of 2,6-Bis(hetaryl)-4-pyrones and 2,6-Bis(hetaryl)-4-pyridinols

Dmitrii L Obydennov; Alena E Simbirtseva; Sergey E Piksin; Vyacheslav Y Sosnovskikh

doi:10.1021/acsomega.0c05357

2,6-Dicyano-4-pyrone as a Novel and Multifarious Building Block for the Synthesis of 2,6-Bis(hetaryl)-4-pyrones and 2,6-Bis(hetaryl)-4-pyridinols

ACS Omega. 2020 Dec 15;5(51):33406-33420. doi: 10.1021/acsomega.0c05357. eCollection 2020 Dec 29.

Authors

Dmitrii L Obydennov¹, Alena E Simbirtseva¹, Sergey E Piksin¹, Vyacheslav Y Sosnovskikh¹

Affiliation

¹ Institute of Natural Sciences and Mathematics, Ural Federal University, 51 Lenina Ave., Ekaterinburg 620000, Russian Federation.

Abstract

In this work, a three-stage and easily scalable synthesis of 2,6-dicyano-4-pyrone (overall yield of 45%) as a new convenient building block has been developed from diethyl acetonedioxalate. It was shown that the transformation with hydroxylamine and [3 + 2]-cycloaddition, in contrast to the reactions with hydrazines, selectively proceed through the attack at the cyano groups without the pyrone ring-opening to give symmetrical and unsymmetrical pyrone-bearing heterocyclic triads containing 1,2,4- and 1,3,4-oxadiazoles as well as tetrazole moieties. The reaction of 2,6-bis(hetaryl)-4-pyrones with ammonia afforded 2,6-bis(hetaryl)pyridines in 63-87% yields. The 4-pyridone/4-pyridinol tautomerism of 2,6-bis(hetaryl)pyridinols and the influence of the nature of adjacent azolyl moieties on this equilibrium have been discussed.