Manganese‐Catalyzed Hydrocarbofunctionalization of Internal Alkenes†

Summary of main observation and conclusion A highly regio‐ and chemo‐selective dimeric Mn(I)‐catalyzed hydroarylation and hydroalkenylation of unbiased internal alkenes with commercially abundant organoboron compounds is reported. A wide range of densely functionalized aliphatic alkenyl amides can successfully undergo site‐exclusive hydrocarbofunctionalization in air atmosphere without any exogenous directing auxiliary, affording an enhanced lead library of structurally diverse γ‐functionalized carboxylic acid derivatives in moderate to good yields. The precise chemoselectivity of the reaction among multiple alkene units even in the presence of reactive terminal alkenes highlights the unique catalytic features of manganese catalyst, and the excellent functional group compatibility of primary amides further complements other transition metals.