Stepwise synthesis of 1,19-dibromo-a,c-biladienes and their conversion into biliverdins, corroles and azaporphyrins

Pandey, Ravindra K.; Zhou, Huanghai; Gerzevske, Kevin R.; Smith, Kevin M.

doi:10.1039/c39920000183

Cited by 16 publications

(10 citation statements)

References 3 publications

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“…Aiming to simplify this synthetic strategy, Smith and co-workers examined the possibility of the in situ 1,19-dibromo- a,c -biladiene synthesis via tripyrrane 17 as an intermediate. Luckily, the stepwise reaction of dipyrrane dicarboxylic acid derivative 15 with equivalents of 2-bromo-5-formyl-3,4-dimethylpyrrole ( 16 ) in the presence of p -toluenesulfonic acid afforded corresponding a,c -biladiene 18 in 50% overall yield, which was smoothly transformed into the expected corrole 19 (Scheme ).…”

Section: β-Substituted Corrolesmentioning

confidence: 99%

Synthesis of Corroles and Their Heteroanalogs

2016

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Corroles have come a long way from being a curiosity to being a mainstream research topic. They are now regularly synthesized in numerous research laboratories worldwide with diverse specific aims in mind. In this review we present a comprehensive description of corroles' synthesis, developed both before and after 1999. To aid the investigator in developing synthetic strategies, some of the sections culminate in tables containing comparisons of various methodologies leading to meso-substituted corroles. The remaining challenges are delineated. In the second part of this review, we also describe the syntheses of isocorroles and heteroanalogs of corroles such as triazacorroles (corrolazines), 10-heterocorroles, 21-heterocorroles, 22-heterocorroles, N-confused corroles, as well as norcorroles. The review is complemented with a short outlook.

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Section: β-Substituted Corrolesmentioning

confidence: 99%

Synthesis of Corroles and Their Heteroanalogs

2016

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“…13 Moreover, if the a,c-biladiene is not functionalized at the tetrapyrrole termini (i.e., the 1- and 19-positions), decomposition often proceeds via cyclization to yield the corresponding aromatic corrole macrocycle. 14–17 …”

Section: Introductionmentioning

confidence: 99%

“…For instance, a,c-biladiene derivatives (Chart ), in which two protons are connected to an sp 3 -hybridized meso -position bisecting the molecule, can rapidly decompose in the presence of air . Moreover, if the a,c-biladiene is not functionalized at the tetrapyrrole termini (i.e., the 1- and 19-positions), decomposition often proceeds via cyclization to yield the corresponding aromatic corrole macrocycle. − …”

Section: Introductionmentioning

confidence: 99%

Electrochemical, Spectroscopic, and¹O₂Sensitization Characteristics of Synthetically Accessible Linear Tetrapyrrole Complexes of Palladium and Platinum

et al. 2017

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The synthesis, electrochemistry, and photophysical characterization of a 10,10-dimethyl-5,15-bis(pentafluorophenyl)-biladiene (DMBil1) linear tetrapyrrole supporting PdII or PtII centers is presented. Both of these nonmacrocyclic tetrapyrrole platforms are robust and easily prepared via modular routes. X-ray diffraction experiments reveal that the Pd[DMBil1] and Pt-[DMBil1] complexes adopt similar structures and incorporate a single PdII and PtII center, respectively. Additionally, electrochemical experiments revealed that both Pd[DMBil1] and Pt[DMBil1] can undergo two discrete oxidation and reduction processes. Spectroscopic experiments carried out for Pd[DMBil1] and Pt[DMBil1] provide further understanding of the electronic structure of these systems. Both complexes strongly absorb light in the UV–visible region, especially in the 350–600 nm range. Both Pd[DMBil1] and Pt[DMBil1] are luminescent under a nitrogen atmosphere. Upon photoexcitation of Pd[DMBil1], two emission bands are observed; fluorescence is detected from ~500–700 nm and phosphorescence from ~700–875 nm. Photoexcitation of Pt[DMBil1] leads only to phosphorescence, presumably due to enhanced intersystem crossing imparted by the heavier PtII center. Phosphorescence from both complexes is quenched under air due to energy transfer from the excited triplet state to ground state oxygen. Accordingly, irradiation with light of λ ≥ 500 nm prompts Pd[DMBil1] and Pt[DMBil1] to photosensitize the generation of 1O2 (singlet oxygen) with impressive quantum yields of 80% and 78%, respectively. The synthetic accessibility of these complexes coupled with their ability to efficiently photosensitize 1O2 may make them attractive platforms for development of new agents for photodynamic therapy.

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“…The synthesis of tetrapyrrolic macrocycles can be easily achieved by cyclization of a proper linear precursor: since a variety of substitution patterns can be introduced in linear tetrapyrroles, a wide range of symmetrically and asymmetrically substituted macrorings is now accessible. The nature of the product of the cyclization reaction depends on the substitution pattern at the 1,19-positions; thus, corroles can be obtained via cyclization of 1,19-dibromo, 1,19-diiodo, and 1,19-diunsubstituted a,c-biladienes. − In the latter case the reaction proceeds through the base-catalyzed formation of an aromatic intermediate, bilatriene, which then generates the direct pyrrole−pyrrole link.…”

Section: Introductionmentioning

confidence: 99%

Acid-Catalyzed Cyclization of 1,19-Unsubstituted a,c-Biladienes

1998

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A new route for the synthesis of corroles through cyclization of a,c-biladienes in acidic media is reported. Spectroscopic analysis of the reaction mixture shows that it proceeds with an intramolecular pathway through the formation of a totally conjugated open-chain tetrapyrrole. The presence of substituents at the 10-position of the tetrapyrrole strongly influences the fate of the reaction: phenyl groups accelerate the cyclization to corrole, whereas in the presence of alkyl substituents this reaction does not occur. This effect has been examined by means of computational methods, and it has been demonstrated that conformational factors are dominant in driving the reaction toward the formation of the macrocycle

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Stepwise synthesis of 1,19-dibromo-a,c-biladienes and their conversion into biliverdins, corroles and azaporphyrins

Cited by 16 publications

References 3 publications

Synthesis of Corroles and Their Heteroanalogs

Synthesis of Corroles and Their Heteroanalogs

Electrochemical, Spectroscopic, and¹O₂Sensitization Characteristics of Synthetically Accessible Linear Tetrapyrrole Complexes of Palladium and Platinum

Acid-Catalyzed Cyclization of 1,19-Unsubstituted a,c-Biladienes

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Stepwise synthesis of 1,19-dibromo-a,c-biladienes and their conversion into biliverdins, corroles and azaporphyrins

Cited by 16 publications

References 3 publications

Synthesis of Corroles and Their Heteroanalogs

Synthesis of Corroles and Their Heteroanalogs

Electrochemical, Spectroscopic, and1O2Sensitization Characteristics of Synthetically Accessible Linear Tetrapyrrole Complexes of Palladium and Platinum

Acid-Catalyzed Cyclization of 1,19-Unsubstituted a,c-Biladienes

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Electrochemical, Spectroscopic, and¹O₂Sensitization Characteristics of Synthetically Accessible Linear Tetrapyrrole Complexes of Palladium and Platinum