Survey of Synthetic Routes towards Phosphorus Substituted Porphyrins

Abstract

This brief review summarizes the synthetic approaches towards porphyrins bearing a C-P bondКлючевые слова: Фосфорилпорфирины, катализируемые переходными металлами реакции кросс-сочетания, образование связи C-P, пиррол, фосфор.

Insights into the Synthesis and the Solution Behavior of meso‐Aryloxy‐ and Alkoxy‐Substituted Porphyrins

“…[10] However, nucleophilic aromatic substitution (S N Ar) reactions usually require drastic conditions to proceed. [13][14][15][16][17][18][19][20][21] Therefore, transition-metalcatalyzed reactions were developed as an alternative route to carry out the reactions of haloporphyrins with nucleophiles [11,12,[22][23][24][25][26][27][28] but these reactions also suffer serious drawbacks such as a limited substrate tolerance, the need for specific and expensive ligands, high catalyst loading and time-consuming optimization of experimental conditions; furthermore, difficulties are encountered in reproduction and upscale experiments, and because of contamination of products by toxic metals. For these reasons, it is perhaps not surprising that S N Ar reactions as a tool for the preparation of C-, O-, S-and N-substituted porphyrins have recently been revisited.…”

Effect of the anchoring group in porphyrin sensitizers: phosphonate versus carboxylate linkages

“…9 The present review has been dedicated to establish the effect of the anchoring group nature in porphyrin sensitizers mainly based on comparative studies of phosphonate versus carboxylate linkages.…”

“…9 These A 4 , A 3 B, A 2 B 2 meso-and β -porphyrins exhibit a priori new and novel chemical and physical properties. More specifically it was already shown that the selfaggregation of metal complexes of (dialkoxy)porphyrins observed in solution and in solid state affords discrete supramolecular architectures or 1D and 2D networks.…”

Advances in Tetrapyrrolic Chemistry over 2013-2017 of Research group Headed by Full Member of RAS A. Yu. Tsivadze: Highlights on the Occasion of his Anniversary

“…Survey of synthetic routes towards phosphorus substituted porphyrins. [14] Figure 12. General and scalable approach to A 2 B-and A 2 BC-type porphyrin phosphonate diesters.…”

“…These compounds, being air-stable and soluble in most organic solvents, are valuable synthetic intermediates because they can be readily transformed into functionalized trans-A 2 BCtype porphyrins through regioselective functionalization at the unsubstituted meso-position of the macrocycle. Therefore, this approach offers considerable promise for application to the synthesis of trans-A 2 BC-type porphyrins, including water-soluble derivatives, push-pull chromophores and bis(porphyrin)s. [13,14] Two series of diphosphoryl-substituted porphyrins were synthesized and characterized by electrochemistry and spectroelectrochemistry. The free-base and five metalated porphyrins with nonredox active centers undergo two ring-centered oxidations and two ring-centered reductions, the latter of which is followed by a chemical reaction of the porphyrin dianion to give an anionic phlorin product ( Figure 13).…”