Coenzyme B12 or adenosylcobalamin, commonly known as Vitamin B12, is one of the most complicated natural organic compounds involved in heteroatom elimination and carbonskeleton rearrangement reactions. Diol dehydratase is an adenosylcobalamin-dependant enzyme that catalyzes conversion from 1, 2-diol compounds to the corresponding aldehydes. Comparison of the structures of the enzyme of substrate-bound and substrate-free forms reveals the activation mechanism of adenosylcobalamin. Structural studies of chiral substrates imply that this enzyme catalyses each enantiomer with different mechanisms in the final step of the reaction.