Synthesis of new glycoporphyrin derivatives through carbohydrate-substituted α-diazoacetates

Abstract

The reaction of carbohydrate-substituted α-diazoacetates with meso-tetrakis(pentafluorophenyl)porphyrinatozin(II) allows the synthesis of new glyco-hydroporphyrin derivatives.

Glycosylated Porphyrins, Phthalocyanines, and Other Porphyrinoids for Diagnostics and Therapeutics

“…245 The major products of these reactions are chlorins, which, when acidified, afford the corresponding free bases with deprotected sugar units (Figure 31). These chlorin derivatives are reported to be better singlet oxygen producers than methylene blue (MB).…”

“…Cavaleiro and co-workers 245 made chlorins by reactions of meso -tetrakis(pentafluorophenyl) porphyrinatozinc(II) with α -diazoacetates derived from diacetonides of the glucofuranose (a), monoacetonide of xylofuranose (b), fructopyranose (c), and galactopyranose (d).…”

Synthetic Chlorins, Possible Surrogates for Chlorophylls, Prepared by Derivatization of Porphyrins

“…Subsequent work a generation later employed ZnF 20 TPP , the zinc chelate of H 2 F 20 TPP , in similar chemistry (Scheme ). The products upon carbene insertion encompassed the cyclopropane-fused chlorin isomers (putative 12-Zn5a−d , 12-Zn6a−d ), the bacteriochlorins, and isobacteriochlorins, although all species were not isolated for each carbene precursor ( 12-Zn5a−d and 12-Zn6b were isolated). The novelty of the carbene precursors was the ability to install an acetonide-protected glycosyl unit on the cyclopropyl ring that is integral to the pyrroline motif.…”

Chemical Synthesis and Medicinal Applications of Glycoporphyrins

“…TFA affording 540a-d. Singlet oxygen production studies showed the chlorins 540a-d to be better than the well-known singlet oxygen producer methylene blue with compound 540b providing the best production. No significant difference in Log P was observed, but chlorins 540a and 540c were only slightly more hydrophilic than 540b,d [271] . Similar methods were used by Hirohara et al to study a range of O-glycosylated tetraarylporphyrins and -chlorins, which showed several advantages including reduced dark cytotoxicity, improved water-solubility, better cellular uptake, and sugar-dependent photocytotoxicity [165,261,262,272,273] .…”

“…All glycosylated chlorins and bacteriochlorins isopropylidene acetals could be deprotected in quantitative yields. Subsequently, this work was extended to azomethine ylides and diazoacetates [271] . A new method for the synthesis of the glyco-conjugates (536-539) was developed using CuCl to catalyze the cyclopropanation reactions of {5,10,15,20-tetra(pentafluorophenyl)porphyrinato}zinc(II) (534) with α-diazoacetates (535a-d) of glucofuranose, fructopyranose, galactopyranose and xylofuranose (Scheme 27).…”