trans‐Selective Aryldifluoroalkylation of Endocyclic Enecarbamates and Enamides by Nickel Catalysis

Abstract Efficient methods for the dicarbofuntionalization of the cyclic alkenes 2‐pyrroline and 2‐azetine are limited. Particularly, the dicarbofunctionalization of endocyclic enecarbamates to achieve fluorinated compounds remains an unsolved issue. Reported here is a nickel‐catalyzed trans ‐selective dicarbofunctionalization of N ‐Boc‐2‐pyrroline and N ‐Boc‐2‐azetine, a class of endocyclic enecarbamates previously unexplored for transition metal catalyzed dicarbofunctionalization. The reaction can be extended to six‐ and seven‐membered endocyclic enamides. A variety of arylzinc reagents and bromodifluoroacetate, and its derivatives, undergo the reaction, providing straightforward and efficient access to an array of pyrrolidine‐ and azetidine‐containing fluorinated amino acids and oligopeptides, which may have applications in the life sciences.