Synthesis of SF5-Substituted Tetrapyrroles, Metalloporphyrins, BODIPYs, and Their Dipyrrane Precursors

The synthesis of novel pentafluorosulfanyl (SF5)-substituted A(4)-type porphyrins, their corresponding Zn--(II) and Pd--(II) metal complexes, A(3)(-), A(2)B- and AB(2)-type corroles, BODIPYs, and their dipyrrane precursors was studied utilizing commercially available SF5-substituted aryl aldehydes. In addition, the functionalization of SF5-substituted tetrapyrroles was investigated by applying the concept of the nucleophilic aromatic substitution (SNAr) with alcohols and sodium azide onto the pentafluorophenyl moiety of a trans-A(2)B(2)-porphyrin and two corrole derivatives with a mixed substitution pattern involving the SF5 group. This allows a fine-tuning of the properties of these macrocycles through a selective and mild introduction of functional groups, giving access to multifunctionalized SF5-substituted porphyrinoids. As an example, one functionalized corrole was further reacted with an azido-substituted BODIPY via the copper(I)-catalyzed 1,3-dipolar cycloaddition yielding the first corrole-BODIPY heterodimer involving the pentafluorosulfanyl group.