Synthesis of glycosylated zinc (II) 5,15-diphenylporphyrin and zinc (II) 5,10,15,20-tetraphenylporphyrin analogs using Cu-catalyzed azide-alkyne 1,3-dipolar cycloaddition reactions

Synthesis of Porphyrin and Bacteriochlorin Glycoconjugates through CuAAC Reaction Tuning

“…As an extension of our efforts to synthesize carbohydrate porphyrin and phthalocyanines conjugates (CPC's and CPcC's respectively), we sought to use a similar copper(I)‐catalyzed 1,3‐dipolar cycloaddition protocol to create CPCs without the use of a “spacer” (Scheme ). Our initial objective was to employ alkynylated porphyrin‐based scaffolds, such as (5‐ethynyl‐10,20‐diphenyldiporphinato)zinc(II) and [5,15‐bis(ethynyl)‐10,20‐diphenylporphinato]zinc(II) (mDPP, 1 , and dDPP, 2 , respectively) and (2‐ethynyl‐5,10,15,20‐tetraphenylporphinato)zinc(II) (bTPP, 3 [19b], in combination with acetate‐protected glycosyl azides ( 4–7 ) as seen in Scheme .…”

“…For example, in our earlier work we explored the feasibility of synthesizing CPCs using click chemistry. Reactions between Zn(II) 5,15‐[ p ‐(ethynyl)‐diphenyl] or Zn(II) 5,10,15,20‐[ p ‐(ethynyl)‐diphenyl] porphyrins and a series of readily available acetate protected glycosyl azides provided the corresponding glycoconjugates in high yields …”

“Click”-reaction: An alternative tool for new architectures of porphyrin based derivatives

“…These kinds of conjugates are used as artificial photosynthetic systems due to photoinduced electron transfer. Compound Carbohydrate porphyrin conjugates (CPCs) 33-36 were synthesized due to their ability to serve as water soluble catalysts and therapeutics for PDT [100]. However, the synthesis of these compounds continues to be a significant challenge, therefore copper catalyzed "click chemistry" was used in order to prepare these molecules.…”

Synthesis and Characterization of Novel Fluoro‐glycosylated Porphyrins that can be Utilized as Theranostic Agents

“…In addition, the synthetic methodology to render the desired carbohydrate‐functionalized porphyrins must be robust and allow for late‐stage conjugation of the sugar modalities, so as to avoid multiple linear synthetic routes. Literature reports on the synthesis of glycosylated porphyrins include both porphyrin formation from the acid‐catalyzed condensation of sugar‐functionalized aldehydes with pyrrole and a coupling reaction between sugar units and an already mature porphyrin . Herein, we present synthetic routes that can be utilized to achieve heterobifunctional glycoconjugated porphyrins with two different sugar moieties, a common monosaccharide (glucose, galactose or N ‐acetyl glucosamine) at three sites, and an FDG moiety at the fourth site (Figure B).…”

“…Herein, we present synthetic routes that can be utilized to achieve heterobifunctional glycoconjugated porphyrins with two different sugar moieties, a common monosaccharide (glucose, galactose or N ‐acetyl glucosamine) at three sites, and an FDG moiety at the fourth site (Figure B). As azide alkyne Huisgen cycloaddition, whereby molecular moieties can be added together by using a copper(I) catalyst at room temperature, has been used by several groups to link carbohydrates to tetrapyrrolic species, the heterobifunctional porphyrinic starting material holds two types of singly addressable terminal attachment points that can be functionalized with desired azide‐functionalized carbohydrate moieties (Figure B). From a photophysical perspective, the glycoporphyrins were demonstrated to display fluorescent properties for optical imaging as well as the generation of singlet oxygen.…”