Regioselective halogenation and palladium-catalysed couplings on 5,15-diphenylporphyrin

Abstract

<jats:p> 5,15-Diphenylporphyrin was regiospecifically halogenated in high yield to give 5-iodo-15-bromo-10,20-diphenylporphyrin, which was then subjected to Heck and Stille-type coupling reactions to form unsymmetrically substituted porphyrins. The regioselectivity of the iodination of diphenylporphyrins and subsequent formation of amphiphilic porphyrins via palladium-based methodology was also studied. The utility of this method for the synthesis of photodynamic sensitisers has been demonstrated on AR4-2J rat pancreatic carcinoma cells. </jats:p>

General and Scalable Approach to A2B‐ and A2BC‐Type Porphyrin Phosphonate Diesters

“…Accordingly, our experimentation began with a revisiting of the monobromination of 5,15‐diarylporphyrins (Scheme ). Encouraged by the preparation of phenyl‐ and 3,5‐di‐ tert ‐butylphenyl‐substituted meso ‐monobromides M2 in 50–60 % yields in reactions between the corresponding free‐base 5,15‐diarylporphyrins M1 and stoichiometric amounts of NBS in chlorinated solvents,, we investigated this reaction with the expectation of improving the yield of M2 formation through a balanced reduction of the yields both of unreacted M1 and of meso ‐dibrominated product M4 . The results are summarized in Table S1 in the Supporting Information.…”

Regioselective 15-Bromination and Functionalization of a Stable Synthetic Bacteriochlorin

“…The bromination or iodination was performed according to literature procedures that have been employed for porphyrins or chlorins. [12][13][14][15] The bromination of H-BC (5substituent ) H) with NBS (1 equiv) in CHCl 3 (1% pyridine) was examined. The reaction was complete at room temperature within 10 min.…”

Synthesis and Functionalization of Porphyrins through Organometallic Methodologies

“…233 The authors reported the synthesis of an acetylene-linked porphyrin dimer in 70% yield through a reaction between meso- . 234 Sonogashira coupling reactions at the β-positions using βhaloporphyrins as substrates were reported by the group of van Lier. 235 Osuka and co-workers also prepared porphyrin bistriflate 22.3Ni through iridium-catalyzed direct borylation.…”