Unveiling Na2-Eosin Y-Catalyzed and Water-Assisted Visible-Light Activation of Oxygen Molecules for the Dicarbonylation of Pyrazole Amines.

Abstract

A novel approach employing visible light-mediated activation of triplet oxygen molecules has been established. The reaction occurs at room temperature between pyrazole amine and phenylglyoxal monohydrate in the presence of Na2-eosin Y. Water played the dual role of solvent and reagent/additive. Photoactivation of triplet oxygen species was used to demonstrate the initiation of the hydrogen atom transfer (HAT) process. The conversion of the reaction mixture was found to be dependent on the amount of water present. Control experiments confirmed the importance of light, the photocatalyst, oxygen, the base, and water. The process tolerated various substitutions in both pyrazole amine and phenylglyoxal derivatives, enabling the synthesis of various dicarbonylpyrazole amines 15 and pyrazolooxazine derivatives 16 in moderate to good yields. 2 equiv of phenylglyoxal 10 gave a different reaction pathway, yielding highly diastereoselective pyrazolooxazine derivatives, confirmed by X-ray diffraction analysis. Collectively, this sustainable and environmentally friendly synthetic technique offers a promising method for the efficient preparation of pyrazole-based heterocyclic compounds. The high regioselectivity observed during the formation of trans-tetrahydropyrazolo[3,4-d][1,3]oxazine has been clarified through computational methods. These investigations emphasize the underlying factors and mechanisms that encourage the formation of this specific product, providing valuable insights into the reaction's selectivity and efficiency.