Pd-Catalyzed Semmler–Wolff Reactions for the Conversion of Substituted Cyclohexenone Oximes to Primary Anilines

Homogeneous Pd catalysts have been
identified for the conversion
of cyclohexenone and tetralone O-pivaloyl oximes
to the corresponding primary anilines and 1-aminonaphthalenes. This
method is inspired by the Semmler–Wolff reaction, a classic
method that exhibits limited synthetic utility owing to its forcing
conditions, narrow scope, and low product yields. The oxime N–O
bond undergoes oxidative addition to Pd0(PCy3)2, and the product of this step has been characterized
by X-ray crystallography and shown to undergo dehydrogenation to afford
the aniline product.