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

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(C₂ H₄ Pⁱ Pr₂ )₂ ]] 1 ([HN(C₂ H₄ Pⁱ Pr₂ )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.