Functionalisation of unactivated methyl groups through cyclopalladation reactions

The transformation of the organopalladium compound (3) into the corresponding deuteriated, chlorinated, or oxidized derivatives (7), (8), or (9), (11), and (12) respectively. is described. The palladation of compound (9) takes place regioselectively leading to the palladated system (13), which is transformed into the difunctionalised oximes (15) and (16). The palladation of $\text{E}$-2,2-dimethyl and 2,2,6,6-tetramethyl-cyclohexanone oxime leads to the corresponding organopalladium compounds (17) and (27), which through deuteriation or oxidation affords the expected products (21) and (31), or (22), (23), (24), and (32), respectively. The second palladation of the compound (22) takes place on the remaining methyl group yielding the organopalladium derivative (26). Finally, $\text{E}$-lupanone oxime is palladated selectively in the 23-position leading to the organopalladium compound (38); the transformation of this compound into its 23-deuterio and 23-acetoxy- derivatives (41) and (42), respectively is also described. The stereochemistry in the palladatlon of lupanone oxime is deduced from NOE studies at 500 MHz.