Methods and intermediates for the synthesis of porphyrins

A method of making a porphyrin of Formula I:

• wherein:
• A is aryl;
• B is H, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkylalkenyl, cycloalkylalkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkoxy, halo, mercapto, azido, cyano, hydroxyl, nitro, acyl, alkoxy, alkylthio, amino, alkylamino, arylalkylamino, disubstituted amino, acylamino, acyloxy, amide, sulfonamide, urea, alkoxylacylamino, aminoacyloxy, hydrophilic groups, surface attachment groups, cross-coupling groups or bioconjugatable groups;
• R1 is selected from the group consisting of H, alkyl and aryl;
• R2, R3, R4, R5, R7, R8, R9, and R10 are each independently selected from the group consisting of H, halo, loweralkoxy, and loweralkylthio;
• and
• M is a metal or a pair of hydrogen atoms;
• said method comprising:
• (a) condensing (i) a bis(imino)dipyrromethane of Formula II:
• wherein:
• R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, cycloalkylalkenyl, cycloalkylalkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, alkoxy, or acyl;
• and
• A, R1, R2, R3, R4, and R5 are as given above, with (ii) a dipyrromethane of Formula III:
• wherein B, R7, R8, R9 and R10 are as given above in an organic solvent containing a metal salt to produce a reaction product;
• then
• (b) optionally oxidizing said reaction product with an oxidizing agent;
• and then
• (c) optionally demetallating said reaction product to produce the porphyrin of Formula I.