Facile functionalization of a fully fluorescent perfluorophenyl BODIPY: photostable thiol and amine conjugates

Vives, Guillaume; Giansante, Carlo; Bofinger, Robin; Raffy, Guillaume; Guerzo, André Del; Kauffmann, Brice; Batat, Pinar; Jonusauskas, Gediminas; McClenaghan, Nathan D.

doi:10.1039/c1cc13778f

Cited by 43 publications

(46 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[16] In the literature the nucleophilic substitution of the para-fluorine atom in PFP-substituted BODIPYs has been carried out on coresubstituted BODIPYs in DMF at room temperature to obtain in some cases a quantitative yield. [26] Hence, BODIPY 4 was dissolved in DMF, n-butylamine (8 eq.) was added, and the mixture was stirred for one hour at room temperature.…”

Section: Full Papermentioning

confidence: 99%

“…[18b,40] The mesohexakis(pentafluorophenyl)-substituted [26]hexaphyrin was first reported by Cavaleiro et al [41] and later its chemistry and synthesis was investigated in detail by Osuka and coworkers.…”

Section: Full Papermentioning

confidence: 99%

“…[40a] Hexaphyrins involving different substituents are rare. [18c, 42,43] The synthetic scope of [26]hexaphyrin was at first limited to reactions of pyrrole with a few fluorinated aromatic aldehydes. [44] In 2003, Osuka and coworkers published a synthesis starting from PFP-dipyrrane and various aldehydes, involving mostly alkyl-and alkoxy-substituted benzaldehydes.…”

Section: Full Papermentioning

confidence: 99%

“…[41] Following the method by Osuka et al [43] BF 3 ·OEt 2 was used as the catalyst. With the two alkoxysubstituted dipyrranes 10b and 15 only the formation of the purple [26]hexaphyrins 16a and 16b was observed (Scheme 4). On the other hand, with the amino-substituted dipyrrane 2e the blue [28]hexaphyrin 23 was isolated (Scheme 4).…”

Section: Full Papermentioning

confidence: 99%

“…The outcome of two hexaphyrins with a different π-system is in accordance with observations in literature. [9g,45,46] It has been described that the reaction of meso-hexakis(pentafluorophenyl)hexaphyrin with amines yielded the substituted [28]hexaphyrin, whereas the reaction with alcohols gave the expected substituted [26]hexaphyrin. [9g, 45,46] Interestingly, the [28]hexaphyrin 17 is obtained though the amino-substituent is already incorporated in the dipyrrane, suggesting that the simple presence of amino groups in the reaction accounts for the formation of the [28]hexaphyrin system.…”

Section: Full Papermentioning

confidence: 99%

See 4 more Smart Citations

Nucleophilic Aromatic Substitution on Pentafluorophenyl‐Substituted Dipyrranes and Tetrapyrroles as a Route to Multifunctionalized Chromophores for Potential Application in Photodynamic Therapy

Gutsche

Ortwerth

Gräfe

et al. 2016

Chemistry A European J

View full text Add to dashboard Cite

Abstract:The application of porphyrinoids in biomedical fields like photodynamic therapy (PDT) requires the introduction of functional groups to adjust their solubility in the biological environment and to allow a coupling to other active moieties or carrier systems. A valuable motif in this regard is the pentafluorophenyl (PFP)-substituent, as the PFP-group easily undergoes a regiospecific nucleophilic replacement (S N Ar) of the para-fluorine atom by a number of nucleophiles. Here, it is shown that -alternatively to an amino-substitution on the final porphyrinoid or BODIPY -the precursor 5-(PFP)-dipyrrane can be modified with amines (or alcohols). These dipyrranes were transformed into amino-substituted BODIPYs. Condensation of these dipyrranes with aldehydes gives access to trans-A 2 B 2 -porphyrins and -A 2 B-corroles. Using pentafluorobenzaldehyde another para-fluorine atom can be introduced enabling the synthesis of multifunctionalized tetrapyrroles. Furthermore, alkoxy-and amino-substituted dipyrranes were applied to the synthesis of A 3 B 3 -hexaphyrins. With this approach polar porphyrins can be prepared, which exhibit in vitro PDT activity against several tumor cell lines.

show abstract

Section: Full Papermentioning

confidence: 99%

Section: Full Papermentioning

confidence: 99%

Section: Full Papermentioning

confidence: 99%

Section: Full Papermentioning

confidence: 99%

Section: Full Papermentioning

confidence: 99%

See 3 more Smart Citations

Nucleophilic Aromatic Substitution on Pentafluorophenyl‐Substituted Dipyrranes and Tetrapyrroles as a Route to Multifunctionalized Chromophores for Potential Application in Photodynamic Therapy

Gutsche

Ortwerth

Gräfe

et al. 2016

Chemistry A European J

View full text Add to dashboard Cite

show abstract

Synthesis, Characterization, and Investigation of Advanced Biological Properties of Non‐Ionic Group Substituted Water‐Soluble BODIPYs

Sekban,

Kaplan,

Özdemir

et al. 2024

Applied Organom Chemis

View full text Add to dashboard Cite

In this study, glycerol, glycosyl, and tetraethyleneglycol monomethyl ether group substituted BODIPY compounds were successfully synthesized and characterized. The antioxidant, antidiabetic, antibiofilm, microbial cell viability, antimicrobial, antimicrobial photodynamic therapy, and DNA cleavage abilities of the BODIPY derivates were also tested. The highest antioxidant activity at 100 mg/L was 87.12% for BODIPY‐1, 85.61% for BODIPY‐2, and 92.78% for BODIPY‐3. The most effective inhibition of microbial cell viability was obtained for these BODIPY molecules at 100% at 50 and 100 mg/L. It was also observed that these BODIPY molecules exhibited excellent biofilm inhibition activities. The derivates were found to exhibit higher antibiofilm abilities against Staphylococcus aureus compared to Pseudomonas aeruginosa. When the antidiabetic effects of water‐soluble BODIPY compounds were examined, the highest effect was found to be 64.40% for BODIPY‐1 at 200 mg/L.

show abstract

Synthesis, Computational Modeling, and Properties of Benzo‐Appended BODIPYs

Uppal

Fronczek

et al. 2012

Chemistry A European J

View full text Add to dashboard Cite

A series of new functionalized mono- and dibenzo-appended BODIPY dyes were synthesized from a common tetrahydroisoindole precursor following two different synthetic routes. Route A involved the assembly of the BODIPY core prior to aromatization, while in Route B the aromatization step was performed first. In general, Route A gave higher yields of the target dibenzo-BODIPYs, due to the ease of aromatization of the BODIPYs compared with the corresponding dipyrromethenes, probably due to their higher stability under the oxidative conditions (2,3-dichloro-5,6-dicyano-1,4-benzoquinone in refluxing toluene). However, due to the slow oxidation of highly electron-deficient BODIPY 3 c bearing a meso-C(6)F(5) group, dibenzo-BODIPY 4 c was obtained, in 35 % overall from dipyrromethane, only by Route B. Computational calculations performed at the 6-31G(d,p) level are in agreement with the experimental results, showing similar relative energies for all reaction intermediates in both routes. In addition, BODIPY 3 c had the highest molecular electrostatic potential (MEPN), confirming its high electron deficiency and consequent resistance toward oxidation. X-ray analyses of eight BODIPYs and several intermediates show that benzannulation further enhances the planarity of these systems. The π-extended BODIPYs show strong red-shifted absorptions and emissions, about 50-60 nm per benzoannulated ring, at 589-658 and 596-680 nm, respectively. In particular, db-BODIPY 4 c bearing a meso-C(6)F(5) group showed the longest λ(max) of absorption and emission, along with the lowest fluorescence quantum yield (0.31 in CH(2)Cl(2)); on the other hand monobenzo-BODIPY 8 showed the highest quantum yield (0.99) of this series. Cellular investigations using human carcinoma HEp2 cells revealed high plasma membrane permeability for all dibenzo-BODIPYs, low dark- and photo-cytotoxicities and intracellular localization in the cell endoplasmic reticulum, in addition to other organelles. Our studies indicate that benzo-appended BODIPYs, in particular the highly stable meso-substituted BODIPYs, are promising fluorophores for bioimaging applications.

show abstract

Facile functionalization of a fully fluorescent perfluorophenyl BODIPY: photostable thiol and amine conjugates

Abstract: Selective nucleophilic substitution on a perfluorophenyl unit comprising a BODIPY fluorophore using an alkanethiol or a primary amine offers a quantitative fluorophore labelling strategy, while retaining high photostability and emission quantum yields approaching unity.

Cited by 43 publications

References 30 publications

Nucleophilic Aromatic Substitution on Pentafluorophenyl‐Substituted Dipyrranes and Tetrapyrroles as a Route to Multifunctionalized Chromophores for Potential Application in Photodynamic Therapy

Nucleophilic Aromatic Substitution on Pentafluorophenyl‐Substituted Dipyrranes and Tetrapyrroles as a Route to Multifunctionalized Chromophores for Potential Application in Photodynamic Therapy

Synthesis, Characterization, and Investigation of Advanced Biological Properties of Non‐Ionic Group Substituted Water‐Soluble BODIPYs

Synthesis, Computational Modeling, and Properties of Benzo‐Appended BODIPYs

Contact Info

Product

Resources

About