Pd/C–H2-Catalyzed One-Pot Aromatization–Deoxygenation of Dihydropyridinediones: A Green, Scalable Route to Alkyl Pyridines

Alkyl-substituted pyridines are ubiquitous structural motifs found in natural products, pharmaceuticals, agrochemicals, and functional organic materials. However, their direct synthesis remains challenging because of the electron-deficient nature of the pyridine ring and the harsh conditions typically required for conventional carbonyl-to-alkane reduction. Herein, we report a mild and environmentally benign Pd/C–H2 catalytic system that enables one-pot oxidative aromatization–deoxygenation of dihydropyridinedione derivatives to afford alkyl-substituted pyridines. The transformation proceeds efficiently at room temperature under atmospheric hydrogen pressure using ethanol as a green solvent, delivering the desired products in up to 91% isolated yield. The protocol exhibits broad substrate scope, high chemoselectivity, operational simplicity, and excellent catalyst recyclability. Mechanistic studies, including hydrogen-free control experiments and intermediate isolation, support a sequential Pd-mediated pathway involving oxidative aromatization, stepwise hydrogen-transfer reduction, and final deoxygenation, with water as the sole stoichiometric by-product. This method provides a sustainable and scalable alternative to classical harsh or reagent-intensive deoxygenation strategies for the synthesis of alkyl-substituted pyridines.