Synthesis of alpha-Formylated N-Heterocycles and Their 1,1-Diacetates from Inactivated Cyclic Amines Involving an Oxidative Ring Contraction

A novel synthesis of pyrrolidine-2-carbaldehydes or tetrahydropyridine-2-carbaldehydes from the cascade reactions of N-arylpiperidines or N-arylazepanes is presented. Mechanistically, the formation of the title compounds involves an unprecedented oxidative ring contraction of inactivated cyclic amines via Cu(OAc)(2)/KI/O-2-promoted oxidative cleavage and reformation of the C-N bond. Interestingly, when PhI(OAc)(2) was used in place of KI, 1,1-diacetates of the corresponding aldehydes were directly obtained with good efficiency. To the best of our knowledge, this is the first example of regioselective C(sp(3))-H bond functionalization and C(sp(3))-N bond activation of saturated cyclic amines using copper salt and oxygen.