Ru-catalyzed activation of sp3 C-O bonds: O- to N-alkyl migratory rearrangement in pyridines and related heterocycles

We report a novel strategy for the formal activation of sp(3) C-O bonds under Ru catalysis. In this reaction, an O-alkylpyridine undergoes migratory rearrangement to its corresponding N-alkylpyridone via coordination of the Lewis basic N atom. This transformation represents the first general catalytic approach to O- to N-alkyl migration in N-containing heterocycles. Extension of this methodology to other heterocycles, including O-alkylpyridazines and O-alkylazoles, was achieved.