New Route to Glycosylated Porphyrins via Aromatic Nucleophilic Substitution (SNAr)-Synthesis and Cellular Uptake Studies.

Glycoporphyrins are group of compounds of high value for the purpose of photodynamic therapy and other biomedical applications. Despite great progress in the field, new diversity-oriented syntheses of carbohydrate-porphyrin hybrids are increasingly desired. Herein, we present efficient, mild, and metal-free conditions for synthesis of glycoporphyrins. The versatile nature of the SNAr procedure is presented in 16 examples. Preliminary biological studies have been conducted on the cytotoxicity and cellular uptake of the final molecules.

Isomers of ß,ß-Dinitro-5,10,15,20-tetraphenylporphy-rin Derivatives: Valuable Starting Materials for Further Transformations.

The synthesis, chromatographic isolation, and structure elucidation of ß,ß-substituted isomers of dinitro-5,10,15,20-tetraphenylporphyrin complexes are described. meso-Tetraphenyl-porphyrin chelates (CuII, NiII, CoII) upon reaction wit e.g., itric acid (yellow HNO3, d = 1.52, diluted to 25⁻50%) in CHCl3 formed a mixture of nitro-derivatives with combined yields of ca 80%. This nitration (under optimized conditions: 25⁻30% HNO3, 30⁻40 min, r.t.) can be carried out selectively to give mainly ß,ß-dinitro-compounds in yields of up to 73%. From the above mixtures of five possible regioisomers that can be formed, usually two or three of them were isolated, for which the structures were assigned on the basis of ¹H NMR spectra including COSY and NOESY measure-ments. These types of products are attractive starting materials for synthesis of potential anticancer PDT agents with unique structures, being practically unavailable by any other alternative method.