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

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.

[1]  A. Osuka,et al.  FACILE REGIOSELECTIVE MESO-IODINATION OF PORPHYRINS , 1998 .

[2]  R. Boyle,et al.  Novel and Improved Syntheses of 5,15-Diphenylporphyrin and its Dipyrrolic Precursors , 1998 .

[3]  R. Boyle,et al.  Structure and Biodistribution Relationships of Photodynamic Sensitizers * , 1996, Photochemistry and photobiology.

[4]  R. Boyle,et al.  Iodination and Heck alkynylation of 5,15-diphenylporphyrin. A convenient entry to asymmetrically meso-substituted porphyrins , 1995 .

[5]  D. Dolphin.  1993 SYNTEX AWARD LECTURE : PHOTOMEDICINE AND PHOTODYNAMIC THERAPY , 1994 .

[6]  R. Sheldon.  Metalloporphyrins in catalytic oxidations , 1994 .

[7]  V. S. Lin,et al.  Facile elaboration of porphyrins via metal-mediated cross-coupling , 1993 .

[8]  E. Matthews,et al.  Photodynamic action of sulphonated aluminium phthalocyanine (SALPC) on AR4-2J cells, a carcinoma cell line of rat exocrine pancreas. , 1990, British Journal of Cancer.

[9]  H. Callot,et al.  Unexpected routes to naphtoporphyrin derivatives , 1990 .

[10]  R. Heck,et al.  Palladium-catalyzed alkenylation and alkynylation of polyhaloarenes , 1990 .

[11]  K. Vollhardt,et al.  Formal Insertion of the HCO⊕ Fragment into a Trinuclear Cluster Metal-Carbyne Bond: Synthesis, Structure and Reactivity of Cluster-bound Ethynol† , 1986 .

[12]  John K. Stille,et al.  The Palladium‐Catalyzed Cross‐Coupling Reactions of Organotin Reagents with Organic Electrophiles [New Synthetic Methods (58)] , 1986 .

[13]  A. W. Johnson,et al.  meso-Substitution products of ætioporphyrin I , 1966 .