Manganese(I)‐Catalyzed β‐Methylation of Alcohols Using Methanol as C1 Source

Abstract Highly selective β‐methylation of alcohols was achieved using an earth‐abundant first row transition metal in the air stable molecular manganese complex [Mn(CO) 2 Br[HN(C 2 H 4 P i Pr 2 ) 2 ]] 1 ([HN(C 2 H 4 P i Pr 2 ) 2 ]=MACHO‐ i Pr). The reaction requires only low loadings of 1 (0.5 mol %), methanolate as base and MeOH as methylation reagent as well as solvent. Various alcohols were β‐methylated with very good selectivity (>99 %) and excellent yield (up to 94 %). Biomass derived aliphatic alcohols and diols were also selectively methylated on the β‐position, opening a pathway to “biohybrid” molecules constructed entirely from non‐fossil carbon. Mechanistic studies indicate that the reaction proceeds through a borrowing hydrogen pathway involving metal–ligand cooperation at the Mn‐pincer complex. This transformation provides a convenient, economical, and environmentally benign pathway for the selective C−C bond formation with potential applications for the preparation of advanced biofuels, fine chemicals, and biologically active molecules