Catalytic isomerization of N-allylic substrates with chiral Os3 clusters as potentially enantioselective reaction

It was shown that the [1,2]-double bond migration of N-allylic compounds catalyzed at ambient temperature by the chiral clusters (μ-H)Os3(μ-OCNR1R2)(CO)10, 1, is not accompanied by a cluster-molecule destruction or change of its configuration. Therefore, this catalytic reaction is perspective for its development as an enantioselective process. The key factor in a capability of 1 to produce the activation is the nature of carboxamido ligand. Deuterium label is not transferred from the μ-D or ND positions of the cluster-catalyst (μ-D)Os3(μ-OCNDMe)(CO)10, 1a, to an alkene substrate, indicating that these hydrogen atoms do not take part in the reaction. The proposed reaction mechanism is the prototropic hydrogen transfer and involves the alkene insertion into the OsO bond.