Nucleophilic Aromatic Substitution (S(N)Ar) and Related Reactions of Porphyrinoids: Mechanistic and Regiochemical Aspects

The nucleophilic substitution of aromatic moieties (S(N)Ar) has been known for over 150 years and found wide use for the functionalization of (hetero)aromatic systems. Currently, several “types” of S(N)Ar reactions have been established and notably the area of porphyrinoid macrocycles has seen many uses thereof. Herein, we detail the S(N)Ar reactions of seven types of porphyrinoids with differing number and type of pyrrole units: subporphyrins, norcorroles, corroles, porphyrins, azuliporphyrins, N‐confused porphyrins, and phthalocyanines. For each we analyze the substitution dependent upon: a) the type of nucleophile and b) the site of substitution (α, β, or meso). Along with this we evaluate this route as a synthetic strategy for the generation of unsymmetrical porphyrinoids. Distinct trends can be identified for each type of porphyrinoid discussed, regardless of nucleophile. The use of nucleophilic substitution on porphyrinoids is found to often be a cost‐effective procedure with the ability to yield complex substituent patterns, which can be conducted in non‐anhydrous solvents with easily accessible simple porphyrinoids.