Ambident reactivity of 5-aminopyrazoles towards donor-acceptor cyclopropanes.

Lewis acid-catalysed reactions of donor-acceptor cyclopropanes with 1,3-disubstituted 5-aminopyrazoles were investigated. Under catalysis with gallium(III) chloride, products of the three-membered ring opening via a nucleophilic attack of the exocyclic amino group were obtained in a chemoselective manner. Oppositely, in the presence of scandium(III) triflate, products of either N -alkylation or C (4)-alkylation, or a mixture of both were formed. The products of the C (4) alkylation were transformed in one step into tetrahydropyrazolo[3,4- b ]azepines that are attractive for medicinal chemistry and pharmacology.