Ionic Liquid-Based Chlorins and Type III Mechanism of Photodynamic Therapy (PDT)

Yoon, Il; Demberelnyamba, D.; Li, Jia Zhu; Shim, Young Key

doi:10.1142/9789814417297_0010

Cited by 3 publications

(4 citation statements)

References 164 publications

(236 reference statements)

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“…The reaction was carried out with 10 equiv of the alkyl bromide. One alkyl bromide that was employed contained an MEM-protected hydroquinone (7)(8)(9)(10)(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22); a second contained estrogen with MEMprotection of the phenol group (7-23). In the former case, one side reaction entailed ester formation between unveiled carboxylates of the chlorin and the hydroquinone bromide.…”

Section: Chemical Reviewsmentioning

confidence: 99%

“…seco-Porphyrazines. Barrett, Hoffman and coworkers performed a fairly standard porphyrazine synthesis by reaction of 2,3-bis(dimethylamino)maleonitrile (14)(15)(16)(17)(18)(19)(20)(21)(22) in the presence of magnesium propoxide in refluxing propanol (Scheme 232). The product was the magnesium porphyrazine 14-Mg23 along with a trace of a more polar pigment, the free base seco-porphyrazine 14-H 2 24.…”

Section: Heteroatoms In the Peripheral Skeletonmentioning

confidence: 99%

“…Semisynthesis − typically begins with the richly abundant molecules chlorophyll a (paths 3a-c) or heme (shown as hemin, path 3d). Transformations of chlorophyll a have afforded the versatile chlorin e 6 trimethyl ester (path 3a); a non-natural analogue of the bacteriochlorophyll c-f compounds (path 3b); and the naturally occurring bacteriochlorophyll c (path 3c) .…”

Section: Introductionmentioning

confidence: 99%

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Synthetic Chlorins, Possible Surrogates for Chlorophylls, Prepared by Derivatization of Porphyrins

2016

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Chlorophylls make Earth green, are the central constituents in the engine of photosynthesis, and not surprisingly have garnered immense attention. A chlorin, the core chromophore of a chlorophyll, is a dihydroporphyrin macrocycle that contains one pyrroline ring and three pyrrole rings. The dominant method for the synthesis of chlorins has entailed the derivatization of porphyrins. The present review covers the ostensibly simple conversion of porphyrins, regardless of synthetic or biological origin, to chlorins. The period covered encompasses the entire history since the beginnings of chlorin synthetic chemistry in the early 20th century through 2015. Representative transformations include hydrogenation, cycloaddition, annulation, and diverse "breaking and mending" approaches. Altogether, the synthesis of >1000 chlorins or chlorin-like compounds (containing >50 distinct pyrroline motifs) is described. Such diversity animates the question "what structural features are essential for a chlorin to resemble chlorophyll?" To begin to address the structure-spectrum relationship, > 250 absorption spectra are provided for representative structures. The synthesis and spectral properties of the vast collection of compounds described herein are expected to illuminate the scope to which synthetic chlorins can serve as surrogates for chlorophylls and be exploited in diverse ways.

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Section: Chemical Reviewsmentioning

confidence: 99%

Section: Heteroatoms In the Peripheral Skeletonmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Synthetic Chlorins, Possible Surrogates for Chlorophylls, Prepared by Derivatization of Porphyrins

2016

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“…The inherent architectural complexity of chlorophylls also makes semisynthesis (versus total synthesis) attractive for gaining access to rare chlorophylls. Semisynthesis, which continues to flourish and has been extensively reviewed, − typically begins with chlorophyll a and entails a handful of reactions: (1) derivatization at the 3-vinyl group, (2) transesterification of the 17 3 -ester, (3) 13 2 -ester pyrolysis, (4) demetalation and remetalation, (5) 20-bromination and subsequent Pd-mediated coupling, (6) 13 1 -carbonyl modification, and (7) for chlorophyll b , derivatization of the 7-formyl group. The red circles shown in Scheme indicate the chief sites of modification.…”

Section: Introductionmentioning

confidence: 99%

De NovoSynthesis of Gem-Dialkyl Chlorophyll Analogues for Probing and Emulating Our Green World

2015

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Woodward reported his infamous synthesis of chlorin e 6 trimethyl ester, a known synthetic precursor to chlorophyll a. [59][60][61][62][63][64]124 The work was posited on a half-century of intensive studies by many investigators in tetrapyrrole chemistry and began a decade after the close of Fischer's lifetime of research 125−128 (which included an uncompleted synthetic program directed toward chlorophylls 15 ). Indeed, "he read all the umpteen papers on the chlorophylls written by Willstaẗter and Fischer, including the experimental parts." 129 The Woodward synthesis of chlorin e 6 trimethyl ester required 46 steps, of which 24 were spent on converting the sole precursor, Knorr's pyrrole, to the four pyrroles destined to form rings A−D; 7 additional steps accrued to obtain the dipyrromethanes that constitute the Eastern and Western halves (Scheme 13, the step numbers are identical to those shown in ref 64.). The first step formed the Knorr pyrrole (in several kg quantities), the next 24 steps were divided into four parallel paths, whereas the remaining 21 steps proceeded in linear fashion. Remarkable features of the synthesis include the directed intramolecular joining (via an imine) of the Eastern and Western halves (step 33), construction of the acrylate Scheme 10. Hydrogenation of a Porphyrin to Form a Chlorin Scheme 11. Representative meso-Tetraarylchlorins Scheme 12. Methyl Pyropheophorbide a

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Bioconjugatable synthetic chlorins rendered water-soluble with three PEG-12 groups via click chemistry

Matsumoto

Taniguchi

Lindsey

2020

J. Porphyrins Phthalocyanines

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Chlorins provide many ideal features for use as red-region fluorophores but require molecular tailoring for solubilization in aqueous solution. A chlorin building-block bearing 18,18-dimethyl, 15-bromo and 10-[2,4,6-tris(propargyloxy)phenyl] substituents has been transformed via click chemistry with CH3(OCH2CH[Formula: see text]-N3 followed by Suzuki coupling with 3-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)propanoic acid, thereby installing a water-solubilization motif and a bioconjugatable handle, respectively. In toluene, [Formula: see text]-dimethylformamide (DMF) or water, the resulting facially encumbered free base chlorin exhibits characteristic chlorin absorption ([Formula: see text] [Formula: see text]412, 643 nm) and fluorescence ([Formula: see text] [Formula: see text]645 nm) spectra with only modest variation in fluorescence quantum yield ([Formula: see text] values (0.24, 0.25 and 0.19, respectively). The zinc chlorin derived therefrom exhibits similar spectral constancy ([Formula: see text] [Formula: see text]414 and 613 nm, [Formula: see text] [Formula: see text]616 nm) and [Formula: see text] 0.094, 0.10 and 0.086 in the three solvents. The results together indicate the viability of the molecular design and synthetic methodology to create red-region fluorophores for use in diverse applications.

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Ionic Liquid-Based Chlorins and Type III Mechanism of Photodynamic Therapy (PDT)

Cited by 3 publications

References 164 publications

Synthetic Chlorins, Possible Surrogates for Chlorophylls, Prepared by Derivatization of Porphyrins

Synthetic Chlorins, Possible Surrogates for Chlorophylls, Prepared by Derivatization of Porphyrins

De NovoSynthesis of Gem-Dialkyl Chlorophyll Analogues for Probing and Emulating Our Green World

Bioconjugatable synthetic chlorins rendered water-soluble with three PEG-12 groups via click chemistry

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