Palladium-catalyzed kumada coupling reaction of bromoporphyrins with silylmethyl grignard reagents: Preparation of silylmethyl-substituted porphyrins as a multipurpose synthon for fabrication of porphyrin systems

Article abstract of DOI:10.1021/jo302122f

We have developed an efficient method for preparing silylmethyl-substituted porphyrins via the palladium-catalyzed Kumada cross-coupling reaction of bromoporphyrins with silylmethyl Grignard reagents. We demonstrated the synthetic utility of these silylmethylporphyrins as a multipurpose synthon for fabricating porphyrin derivatives through a variety of transformations of the silylmethyl groups, including the DDQ-promoted oxidative conversion to CHO, CH₂OH, CH₂OMe, and CH₂F functionalities and the fluoride ion-mediated desilylative introduction of carbona-carbon single and double bonds.