Copper‐Catalyzed Reductive Coupling of Nitroalkanes with Aliphatic Grignard/Cerium and Organozinc Reagents for Synthesis of Functionalized Nitrones

This study aims to develop a more efficient, functional‐group‐tolerant approach using stable nitroalkanes and reductive coupling reactions with aliphatic Grignard/cerium and organozinc reagents. The treatment of nitroalkanes with aliphatic Grignard reagents in the presence of a catalytic amount of CuF₂ and stoichiometric amount of CeCl₃ affords various nitrones in good yields as single isomers. The reaction of tertiary nitroalkanes with organozinc reagents affords various functionalized nitrones without CuF₂ or CeCl₃. These reductive coupling reactions proceed without the loss of functional groups such as alkene, alkyne, benzyl ether, chlorine, ester, and nitrile moieties. Nitrones can also be used as precursors for [3+2] cyclizations with electron‐withdrawing alkenes and alkynes.