Convenient syntheses of phthalocyanine and tetrabenzotriazaporphyrin (TBTAP) mono-alkynes; unhindered building blocks for click chemistry and beyond

Unsymmetrical phthalocyanines and related macrocycles are often desirable for covalent construction or the self-assembly of more complex architectures. Terminal alkynes are versatile in this regard because they are amenable to cross-coupling via Sonogashira-type reactions, alkyne-alkyne coupling via Glaser-type couplings, and triazole formation via Click reaction with azides. Here we describe two complementary syntheses to conveniently add a single alkyne onto the phthalocyanine peripheral position and onto the meso-phenyl group of an (aryl)tetrabenzotriazaporphyrin, here providing a remote link point that is insulated from the macrocycle.