AbstractThe palladium‐catalyzed reductive carbonylation oforthoandpara‐substituted nitrobenzenes has proven to be an attractive route for the synthesis of functionalized carbamates. For the Pd(1, 10‐phenanthroline)2(triflate)2catalyst system, the scope of the reaction has been studied. Substrates with electron‐donating substituents at theparaposition were found to decrease the catalytic activity, most probably as a result of their relatively low oxidizing capacity. the selectivity towards the desired carbamate, however, was increased for these substrates. Under the influence of electron‐withdrawing substituents the azoxybenzene and azobenzene derivatives became important side products. Introduction of large steric hindrance at theorthoposition of the nitro substrates gave rise to an interesting side reaction, viz. methoxylation of the aromatic ring. The methoxylation reaction appeared to occur on an intermediate species in the catalytic cycle. Several functionalities have shown to be resistant to the reaction conditions required for the conversion ot the nitro group. Especially with 4‐nitrobenzoic acid, an extremely high activity and selectivity was found, thus yielding a very convenient synthesis forN‐protected amines containing carboxylic