Effects of aldehyde or dipyrromethane substituents on the reaction course leading to meso-substituted porphyrins

Geier, G. Richard; Lindsey, Jonathan S.

doi:10.1016/j.tet.2004.09.081

Cited by 64 publications

(72 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[8a,34] For electron-deficient aldehydes, e.g., pentafluorobenzaldehyde, BF 3 ·OEt 2 is favored due to higher yields of porphyrin. [35] Therefore, we decided to first employ this catalyst for the condensation. Table 3.…”

Section: Full Papermentioning

confidence: 99%

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%

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

“…Both compound classes show a strong absorbance at wavelengths with a deep light propagation in human tissue (red to near infrared region) while being harmless to the organism in their ground state. [25] In addition, electronwithdrawing substituents render the dipyrromethane, or the final porphyrinoid, susceptible to S N Ar (whereas it is known that porphyrins in general are also susceptible to a nucleophilic attack by strong nucleophiles like organolithium reagents [26] ). [12] Boron-dipyrromethenes (BODIPYs) are well established as fluorescence-imaging dyes in diagnostics [13] and share many characteristics with porphyrins and corroles, such as their intense color and fluorescence.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Porphyrinoids, BODIPYs, and (Dipyrrinato)ruthenium(II) Complexes from Prefunctionalized Dipyrromethanes

et al. 2019

View full text Add to dashboard Cite

The introduction of functional groups into the meso‐position of dipyrromethanes, boron‐dipyrromethenes (BODIPYs) and porphyrinoids, is of fundamental importance in designing such dye systems for material sciences or photomedicine. One route that has proven to be particularly useful in this respect is the nucleophilic aromatic substitution (SNAr) on porphyrinoids and their precursors carrying electron‐withdrawing substituents. To further expand this methodology, the potential of the 4‐fluoro‐3‐nitrophenyl and the 3,4,5‐trifluorophenyl moieties for the synthesis of functionalized dipyrromethanes, BODIPYs, and porphyrinoids has been evaluated. The 3,4,5‐trifluorophenyl moiety proved not to be applicable in the SNAr with nucleophiles. The introduction of the 4‐fluoro‐3‐nitrophenyl group, however, allowed fast and efficient SNAr with various amine nucleophiles. The synthesized 4‐amino‐3‐nitrophenyl‐substituted dipyrromethanes were successfully applied in the synthesis BODIPYs and were tested in the synthesis of “trans”‐A2B2 porphyrins and A2B corroles. Furthermore, the dipyrromethanes – after oxidation to the dipyrromethenes – were found to be suitable ligands for metal ions giving access to functionalized ruthenium(II) metal complexes.

show abstract

“…Zinc porphyrins 1 and 2 have been synthesized following standard protocols for symmetrical [76] A 4 and trans -disubstituted [77] A 2 B 2 meso -functionalized porphyrins. The tetrabrominated core 1 was synthesized from aldehyde 3 and pyrrole ( 4 ) to form the free base porphyrin 5 , which is subsequently converted into its zinc complex 1 .…”

Section: Resultsmentioning

confidence: 99%

Discrete multiporphyrin pseudorotaxane assemblies from di- and tetravalent porphyrin building blocks

Lohse¹,

Krbek²,

Radunz³

et al. 2015

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

SummaryTwo pairs of divalent and tetravalent porphyrin building blocks carrying the complementary supramolecular crown ether/secondary ammonium ion binding motif have been synthesized and their derived pseudorotaxanes have been studied by a combination of NMR spectroscopy in solution and ESI mass spectrometry in the gas phase. By simple mixing of the components the formation of discrete dimeric and trimeric (metallo)porphyrin complexes predominates, in accordance to binding stoichiometry, while the amount of alternative structures can be neglected. Our results illustrate the power of multivalency to program the multicomponent self-assembly of specific entities into discrete functional nanostructures.

show abstract

Effects of aldehyde or dipyrromethane substituents on the reaction course leading to meso-substituted porphyrins

Cited by 64 publications

References 22 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 of Porphyrinoids, BODIPYs, and (Dipyrrinato)ruthenium(II) Complexes from Prefunctionalized Dipyrromethanes

Discrete multiporphyrin pseudorotaxane assemblies from di- and tetravalent porphyrin building blocks

Contact Info

Product

Resources

About