Revisiting 2,3-diaminoporphyrins: key synthons for heterocycle-appended porphyrins

Imidazoporphyrins as supramolecular tectons: synthesis and self-assembly of zinc 2-(4-pyridyl)-1H-imidazo[4,5-b]porphyrinate

“…Among the methods reported for the preparation of imidazoporphyrins, 14,15,17 we have chosen the condensation of 2,3-dioxochlorin and 4-formylpyridine in the presence of ammonium acetate (Scheme 1). 15 The free-base porphyrin PyPor was synthesized in 61% yield and further converted into the zinc and nickel complexes PyPorZn and PyPorNi.…”

“…28 The synthesis of Ni(II) complex PyPorNi was performed upon reflux of PyPor and Ni(acac) 2 in toluene. 17 The obtained compounds were isolated and purified by column chromatography and characterized by 1 H NMR and UV-vis spectroscopies as well as high resolution ESI mass spectrometry. We succeeded in growing single crystals of PyPorZn by slow diffusion of methanol or ethylacetate into a toluene solution of the complex and performed their X-ray structural analysis ( Figure 1 and S1, Figure 2 and S2).…”

“…Moreover, these compounds can also be obtained in high yields from β,β'-diaminoporphyrins and aldehydes that opens additional possibilities for their structural tuning. 17…”

Functionalized heterocycle-appended porphyrins: catalysis matters

“…17,[23][24][25][26][27][28][29][30][31][32][33] Recently, we developed synthetic strategies towards imidazole-and pyrazine-annulated porphyrins starting from tetrapyrrole dioxo-or diamino-derivatives and aromatic aldehydes. 28,[34][35][36][37][38] The sterically hindered tetrapyrrole was used as a synthetic platform for the development of bifunctionalized linear and angular annulated polyaromatic compounds, water soluble derivatives for biomimetic applications and macrocycles with terminal anchoring groups. 34,38 Furthermore, the latter methodology was implemented for the elaboration of a novel class of heteroleptic sandwich-type lanthanide (porphyrinato)(phthalocyaninates) 39,40 based on heterocycle-appended porphyrin ligands.…”

DFT Evaluation of Reactivity of β-Substituted meso-Bromoporphyrins towards Nucleophilic Substitution

“…[23] Our current research is focused on the development of approaches for the transformation of the periphery of the porphyrin macrocycle by means of metal-promoted methods [25] as well as condensation and substitution transformations. [26][27][28][29] Thus, we have developed approaches for the preparation of meso-alkoxy-and meso-aryloxyporphyrins by means of nucleophilic substitution reaction [26] and performed the quantum-chemical investigation of its selectivity. [23] Thus, in mentioned work we have shown that the application of B3LYP 6-31G* level of theory for the analysis of the characteristics of frontier orbitals allows to estimate the reaction path of the nucleophilic reaction.…”