Palladium-catalyzed Kumada Coupling Reaction of Bromoporphyrins with Silylmethyl Grignard Reagents: Preparation of Silylmethylsubstituted Porphyrins as a Multipurpose Synthon for Fabrication of Porphyrin Systems

摘要

We have developed an efficient method fornpreparing silylmethyl-substituted porphyrins via the palladiumcatalyzednKumada cross-coupling reaction of bromoporphyrinsnwith silylmethyl Grignard reagents. We demonstrated thensynthetic utility of these silylmethylporphyrins as a multipurposensynthon for fabricating porphyrin derivatives throughna variety of transformations of the silylmethyl groups,nincluding the DDQ-promoted oxidative conversion to CHO, CH2OH, CH2OMe, and CH2F functionalities and the fluoridenion-mediated desilylative introduction of carbon−carbon single and double bonds.