Conformationally Driven Ru(II)-Catalyzed Multiple ortho-C–H Bond Activation in Diphenylpyrazine Derivatives in Water: Where is the Limit?

Ru(II)/carboxylate/PPh3 catalyst system enabled the preparation of highly conjugated pyrazine derivatives in water under microwave irradiation. Both nitrogen atoms efficiently dictated cleavage of the ortho-C–H bonds in both benzene rings of 2,3-diphenylpyrazine substrates through chelation assistance. In conformationally more flexible diphenyldihydropyrazine 1, the arylation of four ortho-C–H bonds was possible, while in the aromatic analog 2, the triarylation was the limit.