Synthesis of meso-Polyphosphorylporphyrins and Example of Self-Assembling

Abstract

Pd-catalyzed coupling reactions have been used to prepare meso-phosphorylporphyrins. A 2D metal-organic network formed via P horizontal lineO...Zn axial supramolecular coordination of 5,15-bis(diethoxyphosphoryl)-10,20-diphenylporphyrin is the first example of a 2D framework based on phosphorylporphyrin derivatives.

Survey of Synthetic Routes towards Phosphorus Substituted Porphyrins

“…The four C-P bonds can be formed in a onepot procedure from 43 to give a tetraphosphoryl substituted A 4 type porphyrin 44 (Scheme 18). [30] The yield observed for the preparation of this complex was much higher (68 %) than the yield observed for the phosphorylation of the free base in toluene. [33] The A 2 B 2 type phosphorylated porphyrin 46 was obtained using the same conditions by phosphorylation of the tetrabrominated 45 precursor where two bromine atoms are directly linked to the macrocycle ring and another two bromine atoms through an aryl spacer (Scheme 19).…”

“…Palladium-catalyzed phosphorylations both at the meso position of the porphyrin ring and at the p-bromophenyl substituents were described by Enakieva et al [30][31][32] The A 4 and A 2 B 2 porphyrin types were obtained, the A 2 B 2 type being isolated in modest to good yields depending of the reaction conditions (Scheme 16).…”

“…In the course to prepare porphyrin dimers linked by peripherally fused phosphametallocycles in palladium and platinum series, the same group used the Pd-catalyzed C-P cross-coupling reaction of meso-iodoporphyrins (27,30) with diphenylphosphine in MeCN/THF to produce the corresponding meso-(phosphinyl)porphyrins (31a,b) (Scheme 15). [29] This air sensitive derivative was readily oxidized in air to meso-phosphoryl porphyrin (32a).…”

Transition Metal Catalysis in Porphyrin Modifications

“…[19] Later on the catalytic synthesis of the first porphyrincontaining phosphineoxide was published, [20] followed by the work of Guilard and Tsivadze in which di-and tetraphosphonylated porphyrins were synthesized using Pd(OAc) 2 /PPh 3 catalytic system. [21] As borylated porphyrins were found to be very useful building blocks for the synthesis of covalent porphyrin dimers and oligomers, their synthesis attracted much attention. Pinacol borane and bis(pinacol) borane are the most widely used reagents for this purpose.…”

Quantum-Сhemical Insight into the Reactivity of 5-Bromo-10,20-diaryl-porphyrins towards Nucleophiles

“…[3][4][5][6] Transition metalassisted cross-coupling reactions are widely used for porphyrin functionalization. [5,[7][8][9][10][11][12][13][14][15][16] Notwithstanding their versatility, the palladium-mediated cross-coupling reactions require expensive catalysts and ligands that is a limiting factor for their industrial use, in particular in the medical pharmacology.…”