Subnecto Porphyrins

Abstract

Abstract

Strapped porphyrins, with a covalent linkage of the meso-meso or β-β position, offer dual control over both the peripheral porphyrin environment and degree of macrocycle deformation. The tunability of the threedimensional shape of this scaffold has led to their wide utilization as biomimetic models for the active sites of metalloproteins. Since the inception of strapped porphyrins, there have been expansive investigations into their properties and development of their efficient syntheses. However, despite the plethora of methods that exist today, strapped porphyrins remain challenging molecules to synthesize, with their preparation requiring either tedious multi-step synthesis or shorter synthesis hampered by low yields. Given the continued interest in porphyrin nonplanarity, combined with the emerging utility of nonplanar porphyrins as organocatalysts and enzyme mimics, we exploited the flexibility of the nonplanar macrocycle for the facile one step synthesis of a new class of strapped ‘subnecto’ porphyrins. Given the possibility of tailoring both the deformation profile of the macrocyclic core and the shape of the peripheral environment, this method allows for the total control of the nonplanar porphyrin architecture; hence, providing a springboard for the design of tailored nonplanar porphyrin and related π-curved aromatic systems