Pincer-(NHC)Mn(I)\nComplex-Catalyzed Selective α‑Alkylation\nof Ketones and Nitriles Using Unactivated Alkenyl Alcohols

Construction of C–C bonds\nutilizing challenging\nalkenyl\nalcohols employing first-row transition-metal catalysts is an unexplored\narea. Herein, we report the α-alkylation of ketones and nitriles\nusing unactivated alkenyl alcohols as coupling partners in the presence\nof a phosphine-free pincer-NHC carbene-Mn(I) complex. This catalytic\nsystem was highly effective for the α-alkylation of a wide variety\nof ketones and acetonitriles having aromatic, heteroaromatic, and\naliphatic units in the presence of several reducible functional groups.\nThe practical applicability and synthetic value of this protocol were\ndemonstrated through gram-scale synthesis, evaluation of green chemistry\nmetrics, and functionalization of alkylated products into important\nmolecules. Several control experiments, kinetic studies, and Hammett\nstudies were carried out to understand the reaction mechanism, which\nwas further supported by density functional theory (DFT) calculations.