Microwave-promoted insertion of Group 10 metals into free base porphyrins and chlorins: scope and limitations

Dean, Michelle L.; Schmink, Jason R.; Leadbeater, Nicholas E.; Brückner, Christian

doi:10.1039/b716181f

Cited by 54 publications

(52 citation statements)

References 43 publications

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“…23 cycloaddition with diazafulvenium methide 4, generated in situ from sulfone 3 through thermal extrusion of sulfur dioxide. To improve the hydrophilicity of the complex for application in biological systems, Pt(II)-chlorin 5 was converted into the corresponding dihydroxymethyl derivative 6 using LiAlH 4 as reducing agent (Scheme 1).…”

mentioning

confidence: 99%

Platinum(II) Ring-Fused Chlorins as Near-Infrared Emitting Oxygen Sensors and Photodynamic Agents

Pereira

Laranjo

Casalta-Lopes

et al. 2017

ACS Med. Chem. Lett.

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Novel near-infrared luminescent compounds based on platinum(II) 4,5,6,7-tetrahydropyrazolo[1,5-a]-pyridine-fused chlorins are described. These compounds have high photostability and display light emission, in particular simultaneous fluorescence and phosphorescence emission in solution at room temperature, in the biologically relevant 700−850 nm red and near-infrared (NIR) spectral region, making them excellent materials for biological imaging. The simultaneous presence of fluorescence and phosphorescence emission at room temperature, with the phosphorescence strongly quenched by oxygen whereas fluorescence remains unaffected, allows these compounds to be used as ratiometric oxygen sensors in chemical and biological media. Both steady-state (fluorescence vs phosphorescence intensities) and dynamic (dependence of phosphorescence lifetimes upon oxygen concentration) luminescence approaches can be used. Photocytotoxicity studies against human melanocytic melanoma cells (A375) indicate that these compounds display potential as photosensitizers in photodynamic therapy.

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confidence: 99%

Platinum(II) Ring-Fused Chlorins as Near-Infrared Emitting Oxygen Sensors and Photodynamic Agents

Pereira

Laranjo

Casalta-Lopes

et al. 2017

ACS Med. Chem. Lett.

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“…One way of improving the rate of metalation is the use of microwaves during the synthesis. However, microwave-assisted methods have not obtained high yields of the final product in conventional organic solvents because the higher temperature generated in the reaction medium causes some side reactions (Dean et al 2008). Ionic liquids may be used to avoid that problem.…”

Section: Introductionmentioning

confidence: 99%

“…Due to their high molar absorptivity ([10 5 M -1 cm -1 ), inert metalloporphyrins have been practically applied in many fields (Hambright 2007;Borisov and Vasil'ev 2004;Dean et al 2008). However, the slow rate of incorporation of metal ions into the porphyrin ring is often disadvantageous while synthesizing these complexes.…”

Section: Introductionmentioning

confidence: 99%

A convenient and eco-friendly way to synthesize Pt(II) and Pd(II) porphyrins in ionic liquids by microwave activation

Gunawardhana

Tabata

2010

Environ Chem Lett

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Due to the slow rate of incorporation of inertmetal ions into free-base porphyrins compared to other transition metals, several methods have been proposed to accelerate the rate of metalation. However, these methods have disadvantages such as low yields, difficulties of purification of final products, and environmental effects. To avoid those disadvantages, we reacted Pt(II) and Pd(II) salts with H 2 (TPP), H 2 (TMPyP) 4? , and their b-pyrrole derivatives, H 2 (Br 8 TPP) and H 2 (Br 8 TMPyP) 4? , in 1-butyl-3-methylimidazolium bromide ([bmim] ? Br -) under microwave irradiation. The combination of microwave heating and ionic liquids provides efficient thermal energy transfer among the porphyrins and metal salts. In addition, ionic liquids stabilize charged species as well as their intermediates, due to their high dipole moment and high boiling point. This not only shortens the reaction time but also gives high yields of products at relatively low temperatures, of about 100°C compared to conventional synthesis methods: 150°C for DMF, 190°C for DMSO. Here, we demonstrate that Pt(II)/Pt(II) metalloporphyrins are synthesized at high rates, e.g. 6-30 min for 100% metalation, with high yields of 79-93% in [bmim] ? Br -by microwave activation.

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“…Microwave assisted organic synthesis has became an increasingly popular technique in academic and industrial laboratories because of certain advantages particularly shorter reaction times, minimum solvent requirement, and ease of purification [4][5][6]. Application of microwave power in synthesis, metallation, and substitution reactions of porphyrins is not a new concept [7][8][9]. In the past few years, porphyrin chemistry under microwave heating has been under intense study with significant benefits.…”

Section: Introductionmentioning

confidence: 99%

Microwave‐assisted synthesis, metallation, and duff formylation of porphyrins

Yaseen

Ali

Najeebullah

et al. 2009

Journal of Heterocyclic Chem

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in Wiley InterScience (www.interscience.wiley.com).Microwave assisted synthesis, metallation, and b-formylation of porphyrins is described. All synthetic reactions were carried out on inorganic polymer solid support using microwave energy. It is the first documented application of the Duff reaction in the field of porphyrins and metalloporphyrins. The overall process is simple, easy, and environment friendly. FTIR, UV-visible, elemental analysis, 1 H NMR, and mass spectrometry were used to characterize the compounds.

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Microwave-promoted insertion of Group 10 metals into free base porphyrins and chlorins: scope and limitations

Cited by 54 publications

References 43 publications

Platinum(II) Ring-Fused Chlorins as Near-Infrared Emitting Oxygen Sensors and Photodynamic Agents

Platinum(II) Ring-Fused Chlorins as Near-Infrared Emitting Oxygen Sensors and Photodynamic Agents

A convenient and eco-friendly way to synthesize Pt(II) and Pd(II) porphyrins in ionic liquids by microwave activation

Microwave‐assisted synthesis, metallation, and duff formylation of porphyrins

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