Mechanism of alcohol oxidation by dipicolinate vanadium(V): unexpected role of pyridine

Dipicolinate vanadium(V) alkoxide complexes (dipic)V(V)(O)(OR) (OR = isopropoxide (1), n-butanoxide (2), cyclobutanoxide (3), and α-tert-butylbenzylalkoxide (4)) react with pyridine to afford vanadium(IV) and 0.5 equiv of an aldehyde or ketone product. The role of pyridine in the reaction has been investigated. Both NMR and X-ray crystallography experiments indicate that pyridine coordinates to 1, which is in equilibrium with (dipic)V(V)(O)(O(i)Pr)(pyr) (1-Pyr). Kinetic studies of the alcohol oxidation suggest a pathway where the rate-limiting step is bimolecular and involves attack of pyridine on the C-H bond of the isopropoxide ligand of 1 or 1-Pyr. The oxidations of mechanistic probes cyclobutanol and α-tert-butylbenzylalcohol support a two-electron pathway proceeding through a vanadium(III) intermediate. The alcohol oxidation reaction is promoted by more basic pyridines and facilitated by electron-withdrawing substituents on the dipicolinate ligand. The involvement of base in the elementary alcohol oxidation step observed for the dipicolinate system is an unprecedented mechanism for vanadium-mediated alcohol oxidation and suggests new ways to tune reactivity and selectivity of vanadium catalysts.