Nucleophilic Substitution as a Tool for the Synthesis of Unsymmetrical Porphyrins

Senge, Ma­thias O.

doi:10.1002/chin.200552249

Cited by 3 publications

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“…However, regioselectivity is yet to be achieved in nucleophilic substitutions with pterins. In contrast, regioselectivity has been achieved in nucleophilic substitutions with other sensitizers, such as porphyrins (26).…”

Section: Introductionmentioning

confidence: 99%

Kinetic Control in the Regioselective Alkylation of Pterin Sensitizers: A Synthetic, Photochemical, and Theoretical Study

Walalawela

Vignoni

Urrutia

et al. 2018

Photochem & Photobiology

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Alkylation patterns and excited-state properties of pterins were examined both experimentally and theoretically. 2D NMR spectroscopy was used to characterize the pterin derivatives, revealing undoubtedly that the decyl chains were coupled to either the O4 or N3 sites on the pterin. At a temperature of 70°C, the pterin alkylation regioselectively favored the O4 over the N3. The O4 was also favored when using solvents, in which the reactants had increased solubility, namely N,N-dimethylformamide and N,N-dimethylacetamide, rather than solvents in which the reactants had very low solubility (tetrahydrofuran and dichloromethane). Density functional theory (DFT) computed enthalpies correlate to regioselectivity being kinetically driven because the less stable O-isomer forms in higher yield than the more stable N-isomer. Once formed these compounds did not interconvert thermally or undergo a unimolecular "walk" rearrangement. Mechanistic rationale for the factors underlying the regioselective alkylation of pterins is suggested, where kinetic rather than thermodynamic factors are key in the higher yield of the O-isomer. Computations also predicted greater solubility and reduced triplet state energetics thereby improving the properties of the alkylated pterins as O sensitizers. Insight on thermal and photostability of the alkylated pterins is also provided.

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Section: Introductionmentioning

confidence: 99%

Kinetic Control in the Regioselective Alkylation of Pterin Sensitizers: A Synthetic, Photochemical, and Theoretical Study

Walalawela

Vignoni

Urrutia

et al. 2018

Photochem & Photobiology

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“…In parallel the functionalization of porphyrins through functional group interconversions and direct substitution reactions has progressed dramatically in the past decades [140,143] . This is mainly a result of the use of organolithium [144,145] and transition metal catalyzed reactions [143,146] which now allows the preparation of unsymmetrical ABCD-type meso substituted porphyrins and arrays [139,147,148] . Reports on the synthesis of glycoporphyrins mimic this progress.…”

Section: Porphyrin Chemistrymentioning

confidence: 99%

“…Several parameters were examined including the sugar type, the length of the spacer, and the position of the triazole ring for changes in photobiological properties. All derivatives were synthesized from the precursor 473 which was synthesized previously by a modified Senge procedure [144,252] . It was substituted with 1,3-dibromo propane which was converted to the azido groups or propargyl bromide to provide two different scaffolds 474, 475 for glycosyl conjugations.…”

Section: Organometallic Coupling Reactionsmentioning

confidence: 99%

Chemical Synthesis and Medicinal Applications of Glycoporphyrins

Moylan¹,

Scanlan²,

Senge

2015

CMC

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Abstract:This review presents an in-depth overview of the modification of porphyrins with bioconjugates and their applications in medicine today. Porphyrin bioconjugates ranging from nucleotides to steroids are under active scrutiny. However, carbohydrates have been at the forefront of such research in recent years and offer significant potential. This is attributed to their own selectivity to lectins on the surface of cancer cells and their influence on the amphiphilicity of the porphyrin macrocycle. These characteristics and the tendency of porphyrin photosensitizers to accumulate in tumor tissues make glycoporphyrins promising candidates for use as photosensitizers. Thus, a detailed overview of the synthesis and biological evaluation of glycoporphyrins is given with a particular focus on their applications in photodynamic therapy and their future prospects as drug candidates have been reported.

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“…More significant synthetic advances of Temoporfin related compounds are a consequence of general progress in the synthesis of unsymmetrical porphyrins and (bacterio)chlorins [42,43,44,45,46,47,48,49]. These advances have made it possible to prepare porphyrins with different substituent pattern, e.g., different hydrophobic and hydrophilic groups.…”

Section: Simple Modifications and Formulations Of Mthpcmentioning

confidence: 99%

mTHPC – A drug on its way from second to third generation photosensitizer?

Senge

2012

Photodiagnosis and Photodynamic Therapy

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110

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Nucleophilic Substitution as a Tool for the Synthesis of Unsymmetrical Porphyrins

Abstract: Organic chemistry Z 0200 Nucleophilic Substitution as a Tool for the Synthesis of Unsymmetrical Porphyrins -[39 refs.]. -(SENGE, M. O.; Acc. Chem. Res. 38 (2005) 9, 733-743; Dep. Chem., Trinity Coll., Dublin 2, Ire.; Eng.) -Lindner 52-249

Cited by 3 publications

References 1 publication

Kinetic Control in the Regioselective Alkylation of Pterin Sensitizers: A Synthetic, Photochemical, and Theoretical Study

Kinetic Control in the Regioselective Alkylation of Pterin Sensitizers: A Synthetic, Photochemical, and Theoretical Study

Chemical Synthesis and Medicinal Applications of Glycoporphyrins

mTHPC – A drug on its way from second to third generation photosensitizer?

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