Enantioselective Synthesis of Chiral Cyclopent‐2‐enones by Nickel‐Catalyzed Desymmetrization of Malonate Esters

The enantioselective synthesis of highly functionalized chiral cyclopent‐2‐enones by the reaction of alkynyl malonate esters with arylboronic acids is described. These desymmetrizing arylative cyclizations are catalyzed by a chiral phosphinooxazoline/nickel complex, and cyclization is enabled by the reversible E/Z isomerization of alkenylnickel species. The general methodology is also applicable to the synthesis of 1,6‐dihydropyridin‐3(2H)‐ones. An E/Z thing: The enantioselective synthesis of highly functionalized chiral cyclopent‐2‐enones by the nickel‐catalyzed desymmetrizating arylative cyclization of alkynyl malonate esters is described. Cyclization is enabled by reversible E/Z isomerization of alkenylnickel species. TFE=2,2,2‐trifluoroethanol.