A combination of tandem amine-exchange/heterocyclization and biaryl coupling reactions for the straightforward preparation of phenanthro[9,10-d]pyrazoles.

The tandem amine-exchange/heterocyclization of enaminoketones is successfully applied to the regioselective preparation of a series of new 4,5-diarylpyrazoles by reaction of phenylhydrazine and several 3-N,N-(dimethylamino)-1,2-diarylpropenones. The comparison of a vast array of biaryl coupling procedures provides general, complementary approaches to new phenanthro[9,10-d]pyrazoles. The most efficient procedures for this final step in the construction of the tetracyclic system are based on a Stille-type tandem stannylation-biaryl coupling of o,o'-dihalogenated diarylpyrazoles and an hypervalent iodine-mediated nonphenolic oxidative coupling of nonhalogenated precursors.