Enantioselective Allylic Substitutions with Aliphatic Nitro Compounds

Significance

The breadth of allylic substitution reactions has widened since the complement to traditional palladium chemistry has been enhanced by iridium catalysis to provide chiral, branched products. When the authors tried nitro­methane as the nucleophile, the reaction did not proceed smoothly and thus ethyl nitroacetate was employed. Under optimized conditions, the authors were able to obtain extremely high enantiomeric excesses (>98% ee). They subsequently reported a modified procedure for the decarboxylation of the product via LiI, H₂O, DMF conditions.