Directed C−H Bond Oxidation of Bridged Cycloalkanes Catalyzed by Palladium(II) Acetate

We have developed a synthesis of 1,2‐substituted adamantane carboxylic acids and further bridged cycloalkanes (cage compounds) by palladium acetate‐catalyzed C−H bond oxidation. Acetoxylation of cycloalkane framework was performed using picolylamide as a directing group. Modification of the substrate, ligand design and variation of reaction conditions enabled us to study the mechanism of acetoxylation of aliphatic compounds. Post‐functionalization reactions and cleavage of the directing group were developed. For the first time the synthesis and characterization of a β‐C3‐tri‐substituted adamantane derivatives was achieved. See three: Picolylamide directing group enables Pd(OAc)2‐catalyzed oxidation of cage compounds to β‐acetoxy carboxylic acid derivatives. Synthesis of β‐C3‐tri‐substituted adamantane derivatives was achieved.