SYNTHESES OF NOVEL SUBSTITUTED PORPHYRINS BY THE MERCURATION AND PALLADIUM OLEFIN METHODOLOGY

The palladium(II)-catalyzed carbon-carbon coupling reaction (Heck reaction) has been used to perform the 2,4-disubstitution of zinc(II) 2,4-bismercurated deuteroporphyrin IX dimethyl ester 2 with a variety of unsaturated side chains, to give protoporphyrin IX dimethyl ester derivatives that are terminally substituted on the vinyl groups. While aliphatic olefins have been shown to become coupled to deuteroporphyrin IX dimethyl ester in reasonable yield, more efficient coupling is observed with styrenes, particularly electron-deficient ones. Vi-nylferrocene has also been coupled to deuteroporphyrin, providing access to a variety of differentially metalated deuteroporphyrins. An alternate method for synthesis of styrylporphyrins and chlorins from vinylporphyrins (or vinylchlorins) and arylmercurials is also developed. © 1990, American Chemical Society. All rights reserved.