Cobalt-catalyzed regioselective hydrohydrazination of epoxides

Using an air-stable cobalt catalyst [Cp*Co(1,2-Ph2PC6H4S)(NCMe)]BF4 (1, Cp* = Me5C5-), we have achieved catalytic regioselective hydrohydrazination of epoxides to 1,1-hydrazinoalcohols in an atom-economic manner. The catalysis involves a cobalt-hydrazine intermediate, in which the NH2 group of the hydrazine binds to the metal center, inhibiting its nucleophilic reactivity and allowing the NH group to participate in the regioselective hydrohydrazination.