- Bismuth A3-corroles: Useful precursors for the development of meso- substituted free-base corroles
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Systematic studies on regioselective functionalization reactions employing oxygen-, nitrogen-, and sulfur-containing nucleophiles with bismuth A3-corroles under the influence of a strong non-nucleophilic base are reported. In the case of the thiols and dithiols a high-yielding reaction procedure was established to obtain mono-, di-, and tri-functionalized corroles at room temperature within short reaction times. The described method offers a possibility to attach bifunctional linker molecules to the para-position of the meso-pentafluorophenyl groups at positions 5, 10, and 15 of the corrole macrocycle. The described reaction strategy may serve as a versatile protocol for the covalent binding of corroles to proteins or antibodies and may be utilized to attach corroles on, for example, gold or titanium surfaces to study surface-supported reactions.
- Faschinger, Felix,Aichhorn, Stefan,Himmelsbach, Markus,Schoefberger, Wolfgang
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- Easy preparation of cobalt corrole and hexaphyrin and isolation of new oligopyrroles in the solvent-free condensation of pyrrole with pentafluorobenzaldehyde
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(Matrix presented) Following the discovery that meso-substituted corroles are formed in solvent-free condensation of pyrrole with aldehydes, we demonstrate that a small variation in the methodology is suitable for facile synthesis of cobalt(III) corrole and hexaphyrin. These compounds, as well as three noncyclic products, were fully characterized by spectroscopy and X-ray crystallography.
- Simkhovich, Liliya,Goldberg, Israel,Gross, Zeev
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- Two-Step, One-Flask Synthesis of a Meso-Substituted Phlorin
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A two-step, one-flask reaction of pyrrole with pentafluorobenzaldehyde and acetone was investigated to determine the potential for a streamlined synthesis of a phlorin and/or 5-isocorrole as an alternative to stepwise, dipyrromethanecarbinol routes. Analytical-scale reactions were performed examining the effect of reactant concentration, reactant ratio, acid catalyst (TFA or BF3·OEt2), concentration of acid catalyst, oxidant quantity, and reaction time on the distribution of phlorin and 5-isocorrole as well as three additional porphyrinoids (porphodimethene, porphyrin, and corrole). Phlorin was observed ubiquitously in yields up to 20-26%, whereas 5-isocorrole was not detected. Promising reaction conditions for the one-flask synthesis of the phlorin were performed on a preparative scale. The best reaction condition afforded the phlorin in an isolated yield of 20-21% (249-268 mg). Preliminary attempts to extend the methodology to the preparation of phlorins derived from other ketones resulted in a low yield of phlorin from acetophenone (5%) and no detectable phlorin from benzophenone. The discovery of reaction conditions for the two-step, one-flask synthesis of a phlorin provides easier access to this interesting compound, and provides encouragement for the further study of reactions of pyrrole with an aldehyde and a ketone.
- Kim, Dongjoon,Chun, Hao-Jung,Donnelly, Christopher C.,Geier, G. Richard
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- Microwave-assisted synthesis of corroles
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The recently developed Gross's method for the synthesis of corroles has been modified and successfully applied to the preparation of new free base tris-aryl- and tris-pyrimidyl-corroles using solvent-free conditions and microwave irradiation. Compared to
- Collman, James P.,Decréau, Richard A.
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- Synthesis and characterization of cis-A2B-type meso-triaryl-substituted corroles
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A practical synthesis of cis-A2B-type 5,10,15-triarylcorroles has been developed that involves [2+2]-type acid-catalyzed condensation of 5-aryldipyrromethane and 5-(pentafluorophenyl) dipyrromethane-1-carbinol and subsequent 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) induced oxidative cyclization. All the corroles thus synthesized were structurally well-characterized, and their optical and electrochemical properties were also studied.
- Ooi, Shota,Tanaka, Takayuki,Osuka, Atsuhiro
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- Photodynamic effects induced by meso-tris(pentafluorophenyl)corrole and its cyclodextrin conjugates on cytoskeletal components of HeLa cells
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The aim of this work was to synthesize new corrole β-cyclodextrin conjugates βCD1 (with one β-cyclodextrin moiety) and βCD2 (with two β-cyclodextrin moieties) from 5,10,15-tris(pentafluorophenyl)corrole (TPFC) and to test in vitro the efficacy of these compounds towards tumoral HeLa cells. No dark cytotoxicity was observed for TPFC and βCD1 at the concentration used for PDT cell treatment, even during long incubation periods (24 h). Fluorescence microscopy showed that TPFC and βCD1 accumulate in HeLa cells at lysosomes and in the Golgi apparatus, respectively.The cell survival after the PDT treatment with visible light was dependent on light exposure level and compound concentration. βCD1 was able to penetrate efficiently in the cytoplasm of the HeLa cells. In particular, we have analyzed the photodynamic effect of the corrole derivatives on the microtubules of HeLa cells and the morphological alterations on the mitotic spindle. TPFC and βCD1 caused photocytotoxicity in tumoral HeLa cells and induced a rapid metaphase blockage of cells that also showed clearly altered configurations of the mitotic spindle. The results showed that TPFC has the highest photosensitizing efficiency on tumoral cells.
- Barata, Joana F.B.,Zamarrón, Alicia,Neves, M. Grac? P.M.S.,Faustino, M. Amparo F.,Tomé, Augusto C.,Cavaleiro, José A.S.,R?der, Beate,Juarranz, ángeles,Sanz-Rodríguez, Francisco
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- The First Silicon(IV) Corrole Complexes: Synthesis, Structures, Properties, and Formation of a μ-Oxo Dimer
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The first SiIV corrole complexes were synthesized in good yields by treatment of meso-triarylcorroles with tetrachlorosilane in 1,2-dichloroethane at 60 °C. The central silicon atom possesses a square-pyramidal coordination geometry with slight
- Ueta, Kento,Fukuda, Masaya,Kim, Gakhyun,Shimizu, Soji,Tanaka, Takayuki,Kim, Dongho,Osuka, Atsuhiro
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- Two-Step, One-Flask Synthesis of an N-Confused Porphyrin Bearing Pentafluorophenyl Substituents
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A two-step, one-flask reaction of pyrrole and pentafluorobenzaldehyde was investigated as a streamlined synthetic route to an N-confused porphyrin bearing pentafluorophenyl substituents previously prepared by a stepwise route. A survey of acid catalysts, acid catalyst concentration, DDQ quantity, and reaction time was performed with monitoring by HPLC. The targeted N-confused porphyrin was observed from many reaction conditions. The best condition afforded the N-confused porphyrin in an isolated yield of 10-12% (245-281 mg), providing improved access to this interesting porphyrinoid.
- Fisher, Julia M.,Kensy, Victoria K.,Geier, G. Richard
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- Control of oligomerization and oxidation steps in the synthesis of tris(pentafluorophenyl)corrole
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The mechanistic features of oligomerization and oxidative cyclization steps in the synthesis of tris(pentafluorophenyl)corrole (1) have been thoroughly studied. Separation of the intermediates by preparative HPLC and analysis by NMR spectroscopy and high
- Blumenfeld, Carl,Fisher, Katherine J.,Henling, Lawrence M.,Grubbs, Robert H.,Gray, Harry B.,Virgil, Scott C.
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supporting information
p. 3022 - 3025
(2015/05/13)
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- Corrole and corrole functionalized silica nanoparticles as new metal ion chemosensors: A case of silver satellite nanoparticles formation
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Corrole macrocycles are very appealing dyes for incorporation into light harvesting devices. This work shows the sensorial ability of 5,10,15-tris(pentafluorophenyl)corrole 1 and its monoanionic species toward Na+, Ca2+, Cu2+, Cd2+, Pb 2+, Hg2+, Ag+, and Al3+ metal ions in toluene and acetonitrile. The photophysical studies toward metal ions were carried out by absorption and emission spectroscopy. From all metal ions studied, corrole 1 shows to be colorimetric for Hg2+ allowing a naked-eye detection of Hg2+ through a change of color from purple to blue in acetonitrile and from green to yellow in toluene. In addition a new β-imine corrole 4 was successful synthesized and further functionalized with 3-isocyanatopropyl-trimethoxysilane resulting in an alkoxysilane derivative 5. The grafting of alkoxysilane derivative 5 with optically transparent silica nanoparticles (SiNPs) was achieved succesfully. The new-coated silica nanoparticles with corrole 5 were studied in the presence of Cu2+, Hg2+, and Ag+ as metal ion probes. Interestingly, upon addition of Ag+, groups of satellite AgNPs were formed around the SiNPs and were checked by transmission electron microscopy (TEM). At same time, a change of color from green to yellow was observed.
- Santos, Carla I. M.,Oliveira, Elisabete,Fernandez-Lodeiro, Javier,Barata, Joana F. B.,Santos, Sergio M.,Faustino, M. Amparo F.,Cavaleiro, Jose A. S.,Neves, M. Graca P. M. S.,Lodeiro, Carlos
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p. 8564 - 8572
(2013/09/02)
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- Electron deficient manganese(III) corrole catalyzed oxidation of alkanes and alkylbenzenes at room temperature
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At room temperature electron deficient manganese (III) corrole complexes (1-3) were successfully employed as catalysts in the oxidation of alkanes and alkylbenzenes using m-chloroperbenzoic acid (m-CPBA) as the terminal oxidant. Adamantane has been selectively hydroxylated to adamantane 1-ol and 2-ol with higher preference for the tertiary position. Cyclohexane has also been oxidized. The present oxidizing system also oxidizes toluene, ethylbenzene and diphenylmethane. High valent oxomanganese(V) species has been proposed to be the active oxidant. The high-valent oxomanganese(V) corrole undergoes hydrogen atom transfer (HAT) reaction with 2,4,6-tri-t-butylphenol (TTBP) resulting in the formation of oxidized phenoxyl radicals. Kinetic studies have led to the determination of second-order rate constants for the hydrogen atom transfer reactions. The kinetic experiments reveal a first order reaction rate dependence on the concentration of catalyst as well as on that of the oxidant.
- Bose, Suranjana,Pariyar, Anand,Biswas, Achintesh Narayan,Das, Purak,Bandyopadhyay, Pinaki
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experimental part
p. 1193 - 1197
(2012/01/13)
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- Synthetic, cyclic voltammetric, structural, EPR and UV-vis spectroscopic studies of thienyl-containing meso-A2B-cor(Crv=0) systems: Consideration of three interrelated molecular detection modalities
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We report eight new A2B-type (Mn+) corrolate compounds (two structural studies) that include the oxo[5,15- bis(pentafluorophenyl)-10-R-corrolatochromium(V)] [R = 2-/3-thienyl (1a/2a), 3-thianaphthyl (3a)] species. The first examples of meso-A2 (thienyl)- and Cr-A2B-corrole types are represented herein. Characterization includes cyclic voltammetry, electron paramagnetic resonance, 2D (1H and 13C) NMR, and UV-vis spectroscopy, mass spectrometry, and elemental analysis. Compounds 1a-3a have enabled analyte binding capacity studies. [Cu2+...O=Cr(cor)] binding represents a new selective mode of corrole-based detection, whereas free-base A 2B-corroles exhibited limited Mn+ selectivity. The 10-position substitution affects optical profiles In analyte titrations. A limited amount of PPh3 O-atom uptake from [O=Cr(cor)] was also demonstrated.
- Egorova, Olga A.,Tsay, Olga G.,Khatua, Snehadrinarayan,Meka, Bhupal,Maiti, Nilkamal,Kim, Min-Kyu,Kwon, Seong Jung,Huh, Jung Oh,Bucella, Daniela,Kang, Sa-Ouk,Kwak, Juhyoun,Churchill, David G.
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experimental part
p. 502 - 512
(2010/03/25)
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- Mild oxidation of hydrocarbons by tert-butyl hydroperoxide catalyzed by electron deficient manganese(III) corroles
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Mild oxidations of alkenes with tert-butylhydroperoxide catalyzed by electron deficient manganese(III) corroles have been achieved at room temperature. The oxygenation of cyclohexane, adamantane and toluene has also been studied under similar reaction conditions. The oxidation has been shown to proceed with participation of alkylperoxy (ROO) radicals and organo-hydroperoxide (ROOH). A reaction mechanism is proposed based on the experimental results.
- Bose, Suranjana,Pariyar, Anand,Biswas, Achintesh Narayan,Das, Purak,Bandyopadhyay, Pinaki
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experimental part
p. 1 - 6
(2010/12/25)
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- Efficient synthesis of 5,10,15-triarylcorroles using Amberlyst 15 under solvent-free conditions
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(Chemical Equation Presented) An efficient and convenient synthesis of 5,10,15-triarylcorroles by the condensation of aryl aldehydes with pyrrole catalyzed by Amberlyst 15 followed by oxidative cyclization with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (D
- Kumari, Pratibha,Chauhan, Shive M. S.
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p. 779 - 783
(2008/09/20)
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- Mechanism of catalytic aziridination with manganese corrole: The often postulated high-valent Mn(V) imido is not the group transfer reagent
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The reaction of Arl=NTs (Ar = 2-(tert-butylsulfonyl)benzene and Ts = p-toluenesulfonyl) and (tpfc)Mn (tpfc = 5,10,15-tris(pentafluorophenyl)corrole), 1, affords the high-valent (tpfc)MnV=NTs, 2, on stopped-flow time scale. The reaction proceeds
- Zdilla, Michael J.,Abu-Omar, Mahdi M.
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p. 16971 - 16979
(2007/10/03)
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- A survey of acid catalysis and oxidation conditions in the two-step, one-flask synthesis of meso-substituted corroles via dipyrromethanedicarbinols and pyrrole
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The reaction of dipyrromethanedicarbinols with pyrrole leading to meso-substituted corroles was investigated to determine whether mild acid catalysts [Dy(OTf)3, Yb(OTf)3, Sc(OTf)3, and InCl3] known to provide po
- Geier III, G. Richard,Chick, Jeffrey Forris Beecham,Callinan, Jennifer B.,Reid, Christopher G.,Auguscinski, Waldemar P.
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p. 4159 - 4169
(2007/10/03)
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- Refined methods for the synthesis of meso-substituted A3- and trans-A2B-corroles
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We have refined a one-pot synthesis of A3-corroles via 3+4 condensation of an aldehyde with a pyrrole followed by macrocyclization mediated by DDQ. After thorough examination of various reaction parameters (reactivity of an aldehyde, catalyst, solvent, concentration, time etc.) we have elaborated three different sets of conditions for different types of aromatic aldehydes - highly reactive, moderately reactive and sterically hindered. Thanks to the identification of the key factors influencing the yield of bilanes and the yield of their conversion to corroles we were able to improve yields to ca. 17% for highly reactive aldehydes and ca. 13% for moderately reactive aldehydes. Altogether fourteen A3-corroles have been prepared in 7-21% yield. 5,10,15-Trimesitylcorrole has been obtained for the first time. [2 + 1] Condensation between sterically hindered dipyrromethanes and aldehydes has also been refined and yields of trans-A2B-corroles have been improved by ca. 10%.
- Gryko, Daniel T.,Koszarna, Beata
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p. 350 - 357
(2007/10/03)
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- Electronic absorption, resonance Raman, and electrochemical studies of planar and saddled copper(III) meso-triarylcorroles. Highly substituent-sensitive Soret bands as a distinctive feature of high-valent transition metal corroles
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We present here a first systematic study of substituent effects in metallocorroles, based on electronic absorption, resonance Raman (RR), and infrared (IR) spectroscopic studies and electrochemical measurements on 10 copper(III) meso-triarylcorroles, CuIII[β-Y8TArC], where the β-substituent Y = H or Br and the meso-aryl group Ar = C6F5 or p-X-C6H4 and X = CF3, H, CH3, and OCH3. The results afford a number of significant inisights. (1) The RR (and IR) results show that at least two and possibly more high-frequency bands in the 1400-1550 cm-1 region exhibit significant frequency downshifts on β-octabromination and, thus, qualify as structure-sensitive marker bands. DFT geometry optimizations indicate that the saddled conformation should be clearly preferred for the β-octabromo-meso-triarylcorrole derivatives studied and that β-octabromination results in expansion of a number of skeletal bond distances of the corrole macrocycle, consistent with observed frequency downshifts. (2) Electrochemical measurements on planar CuIII[TArC] derivatives have shown that the para substituents on the meso-aryl groups exert a strong influence on the half-wave potentials for oxidation (ρox = ΔE1/2ox/Δ(3σ) = 95 mV), suggesting that oxidation involves removal of an electron from the corrole "b1" HOMO, which has significant amplitudes at the meso postions and crudely resembles a porphyrin a2u HOMO in shape. In contrast, the Hammett ρox is much lower for the nonplanar CuIII[Br8TArC] derivatives and we suggest that this ultimately results from a b1-to-a2 HOMO reversal which in turn stems from a metal (dx2-y2)-corrole ("b1") orbital interaction that becomes symmetry-allowed under a saddle distortion of the corrole macrocycle. In contrast to what has been observed for metallotetraphenylporphyrins, β-octabromination dramatically raises the half-wave potential for one-electron oxidation of the triarylcorrole derivatives studied. This appears to be due to the fact that both the "a2" and "b1" HOMOs of a corrole (in C2v notation) have significantly higher amplitudes at the β positions, compared to a porphyrin a2u HOMO. Thus, although many metallocorroles are significantly more easily oxidizable than analogous metalloporphyrins, certain β-octahalogeno-meso-triarylcorrole derivatives can indeed be extremely electron deficient and oxidation resistant and may, therefore, find use as rugged catalysts or reagents under highly oxidizing conditions. (3) Finally, the Soret absorption maxima of high-valent metallotriarylcorroles exhibit a uniquely sensitive dependence on the substituents on the meso-aryl groups. Thus, on going from CuIII[T(p-CF3-P)C] (T(p-CF3-P)C = meso-tris((p-trifluoromethyl)phenyl)corrolato) to CuIII[T(p-OM-P)C] (T(p-OM-P)C = meso-tris(p-methoxyphenyl)corrolato), the Soret maximum red shifts by 26 nm, from 407 to 433 nm. Similarly, on going from CuIII[Br8T(p-CF3-P)C] (Br8T(p-CF3-P)C = β-octabromo- meso-tris((p-trifluoromethyl)phenyl)corrolato) to CuIII[Br8T(p-OM-P)C] (Br8T(p-CF3-P)C = β-octabromo-meso- tris(p-methoxyphenyl)corrolato), the Soret maximum red shifts by 34 nm, from 434 to 468 nm. Time-dependent DFT calculations suggest that this substituent dependence reflects significant ligand-to-metal charge-transfer character of certain transitions in the Soret region. The optical spectra of free-base and non-high-valent transition metal tetrapyrroles, in general, do not exhibit a similar substituent dependence.
- Wasbotten, Ingar H.,Wondimagegn, Tebikie,Ghosh, Abhik
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p. 8104 - 8116
(2007/10/03)
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- Synthesis and functionalization of meso-aryl-substituted corroles
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The Rothemund condensation reaction of pyrrole and aldehydes is an extensively used route to meso-tetraarylporphyrins, but simple modifications of the reaction conditions allow the formation of different macrocycles other than the expected porphyrin. In the presence of an excess of pyrrole, this modified Rothemund approach leads to the synthesis of meso-triaryl-substituted corroles. This methodology allows the preparation of a wide range of substituted corroles starting from commercially available products. Higher yields have been obtained in the case of benzaldehydes bearing electron-withdrawing substituents, while the reaction fails in the presence of 2,6-disubstituted benzaldehydes. Although if not isolated, some experimental evidences indicate that the linear 5,10,15-triphenylbilane 4 is the precursor of the final corrole ring. Reaction of 5,10,15-triphenylcorrole 2 with an excess of NBS leads to the complete bromination of the macrocycle. Spectroscopic characterization seems to indicate the formation of the porphodimethene-like structure 5, where the macrocyclic aromatic conjugation is interrupted at the 10 position. Metalation of this compound with cobalt acetate and PPh3 affords the corresponding complex. The X-ray crystal structure of triphenylphosphine [2,3,7,8,12,13,17,18-octabromo-5,10,15-tris(4-nitropheriyl)corrolato]-cobalt( III) 8 confirms the ability of corrole ring to retain an almost planar conformation when fully substituted at the peripheral positions.
- Paolesse,Nardis,Sagone,Khoury
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p. 550 - 556
(2007/10/03)
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