Contracted porphyrins and calixpyrroles: synthetic challenges and ring-contraction effects

Abstract

Ring-contracted porphyrin analogues, such as subporphyrins and calix[3]pyrroles, have recently attracted considerable attention not only as challenging synthetic targets but also as functional macrocyclic compounds. Although canonical porphyrins and calix[4]pyrrole are selectively generated via acid-catalyzed condensation reactions of pyrrole monomers, their tripyrrolic analogues are always missing under similar conditions. Recent progress in synthesis has shown that strain-controlled approaches using boron(III)-templating, core-modification, or ring tightening provide access to various contracted porphyrins. The tripyrrolic macrocycles are a new class of functional macrocycles exhibiting unique ring-contraction effects, including strong boron chelation and strain-induced ring expansion. This Perspective reviews recent advances in synthetic strategies and the novel ring-contraction effects of subporphyrins, triphyrins(2.1.1), calix[3]pyrroles, and their analogous.