In conclusion, we have developed the first versatile and useful approach for the selective reduction of structurally diverse nitrogen-based heteroarenes with ammonia borane as a reducing agent in the presence of a homogeneous Cp2TiCl2 catalyst. The reaction enables a broad functional group tolerance of quinolines under synthetically relevant conditions, which proved useful for complex and medicinally relevant compounds. Particularly, for the first time, we have shown the chemoselective reduction of quinolines-bearing substituents directly on the reducible ring (e.g., Br, Cl, Ph-CF3, PhOCF3, Ph-F, Ph-SO2Me, and styryl derivatives) and many of the isolated corresponding Csp 3 -rich N-heterocycles are elusive in literature. Further, unprotected functionalized pyridines (e.g., Cl, Br, OH, CF3, NH2, CH2-NH2, CH2-OH, Ph-Br, Ph-Cl, Ph-CF3, PhOCF3), indoles, pyrazines, and some selected benzofuran derivatives were also successfully demonstrated, and gram-scale synthesis was also effectively executed. The Ti-catalyst is also viable for the partial reduction of 3-bromoquinoline illustrating a very nice regioselectivity of this approach. DFT calculations support Cp2Ti(III)-H formation as an active species and predict a concerted H + /H -mechanism for the hydrogenation of quinoline. We believe the isolated saturated nitrogenous-based products using ammonia borane and titanium as green catalysts will enhance drug discovery space. The extension of this work to arene systems is in progress and in-depth mechanistic investigations are underway.