Versatile synthesis of meso-aryloxy- and alkoxy-substituted porphyrins via palladium-catalyzed C-O cross-coupling reactions.

[reaction: see text] meso-Aryloxy- and alkoxy-substituted porphyrins were conveniently synthesized by direct reactions of meso-halogenated porphyrins with alcohols via palladium-catalyzed C-O cross-coupling reactions. Using a combination of palladium precursor Pd(OAc)(2) or Pd(2)(dba)(3) and phosphine ligand DPEphos or Xantphos allowed both 5-bromo-10,20-diarylporphyrin and 5,15-dibromo-10,20-diarylporphyrin, as well as their zinc complexes, to be effectively coupled with a variety of alcohols to give the corresponding mono- and bis-substituted meso-aryloxy/alkoxyporphyrins in moderate to high yields under mild conditions.