Part I. Synthesis and synthetic applications of porphyrin cyclobutenediones. Part II. Preparation of organoplatinum compounds for anticancer studies

A general methodology for attaching 3-isopropoxycyclobutene-1,2-dionyl groups to the meso positions of diphenylporphyrin directly or through a double bond has been developed by using Pd-catalyzed cross-coupling reaction of an organotin reagent and free base bromodiphenylporphyrins. The porphyrin cyclobutenedione compounds are very versatile precursors to a variety of porphyrin derivatives. Structurally diverse porphyrin quinones have been synthesized from zincated porphyrin cyclobutenediones. This represents one of the most general and efficient syntheses of porphyrin quinones. Selective bromination of the unsubstituted meso positions of porphyrin cyclobuteriediones followed by Pd-catalyzed cross-coupling reactions afforded a series of highly conjugated porphyrin cyclobutenediones, which have electron push-pull structural characteristics and absorb at long wavelengths. Porphyrin cyclobutenedione amine derivatives were prepared by substitution reactions of the cyclobutenedione isopropoxy group of the porphyrin cyclobutenediones. This reaction might open up a simple and general route to many porphyrin bioconjugates that might find interesting applications in medicine. Porphyrin squaric acids were also prepared from porphyrin cyclobutenediones in high yields. A dimerization reaction forming meso-linked porphyrin dimers has been discovered, which allows easy access to meso-linked porphyrin dimers. Finally, an unusual addition reaction of N-Bromosuccinimide with a vinylporphyrin has been discovered. This reaction might lead to a simple synthesis of a novel class of porphyrin amino acids, which could be useful synthetic blocks for many interesting porphyrins.;An efficient synthetic methodology for preparing platinum(II) diaryl diamine complexes has been developed. However, the corresponding platinum aryl chloro diamine complexes remain elusive.