- Steric control of mesocate and helicate formation: Bulky pyrrol-2-yl Schiff base complexes of Zn2+
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Regioisomerism about a phenyl spacer alters the number of nuclei which participate in self-assembly with pyrrole/schiff base ditopic ligands. The bulky benzyl ester substituents favor formation of di- and tetranuclear (but not trinuclear) complexes. The r
- Gorden, A. E. V.,Gorden, J. D.,Hiti, E. A.,Mayhugh, J. T.,Niklas, J. E.,Wilkinson, G. R.
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supporting information
(2022/01/14)
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- Pyrrophens: Pyrrole-Based Hexadentate Ligands Tailor-Made for Uranyl (UO22+) Coordination and Molecular Recognition
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Derivatives of a novel pyrrole-containing Schiff base ligand system (called "pyrrophen") are presented which feature substituted phenylene linkers (R1 = R2 = H (H2L1); R1 = R2 = CH3 (H2L2)) and a binding pocket modeled after macrocyclic species. These lig
- Forbes, Madeleine G.,Gorden, Anne E. V.,Gorden, John D.,Mayhugh, Jacob T.,Niklas, Julie E.
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- Total synthesis of hematoporphyrin and protoporphyrin; A conceptually new approach
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The total synthesis of protoporphyrin IX and its disodium salt using a new alternative method to the classical MacDonald condensation is reported. The key step is the reaction of the new unsymmetrical diiodo dipyrrylmethane 1 with the known dipyrrylmethane 2. Coupling of the two fragments leads directly to porphyrin 3 without the need of an oxidizing agent. The new methodology is well suited for the synthesis of protoporphyrin IX derivatives on a multi-100 g scale in good quality without the need for chromatography. Furthermore, these preparations are completely free of any contaminant of animal origin, which represents a real improvement in the manufacturing of protoporphyrin IX derivatives. Schweizerische Chemische Gesellschaft.
- Martin, Pierre,Mueller, Markus,Flubacher, Dietmar,Boudier, Andreas,Spielvogel, Dirk
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p. 204 - 206
(2013/07/05)
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- Total synthesis of hematoporphyrin and protoporphyrin: A conceptually new approach
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The total synthesis of protoporphyrin IX and its disodium salt using a new alternative method to the classical MacDonald condensation is reported. The key step is the reaction of the new unsymmetrical diiodo dipyrrylmethane 1 with the known dipyrrylmethane 2. Coupling of the two fragments leads directly to porphyrin 3 without the need of an oxidizing agent. The new methodology is well suited for the synthesis of protoporphyrin IX derivatives on a multi 100 g scale in good quality without the need for chromatography. Furthermore, these preparations are completely free of any contaminant of animal origin, which represents a real improvement in the manufacturing of protoporphyrin IX derivatives.
- Martin, Pierre,Mueller, Markus,Flubacher, Dietmar,Boudier, Andreas,Blaser, Hans-Ulrich,Spielvogel, Dirk
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experimental part
p. 799 - 804
(2011/03/19)
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- Process For Preparing Porphyrin Derivatives, Such As Protoporphyrin (IX) And Synthesis Intermediates
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The present invention relates to a process for preparing a porphyrin of formula (I), optionally in the form of a salt with an alkali metal and/or in the form of a metal complex: in which: R and R′ are as defined in claim 1, comprising: a step of condensation, in an acidic medium, between a dipyrromethane of formula (II): in which R′b is as defined above for (I), and a dipyrromethane of formula (III): in which R″ is as defined in claim 1, and also the compounds of formula (III).
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Page/Page column 12; 16
(2008/12/07)
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- Effect of meso-substituents on the osmium tetraoxide reaction and pinacol-pinacolone rearrangement of the corresponding vic-dihydroxyporphyrins
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To investigate the effects of electron-donating and electron-withdrawing substituents upon the reaction of porphyrins with osmium tetraoxide, and the pinacol-pinacolone rearrangement of the resulting diols, a series of meso-substituted porphyrins were prepared by total synthesis. Porphyrins with electron-donating substitutents at the meso-positions gave vic-dihydroxychlorins in which the adjacent pyrrole subunit was predominantly oxidized. No such selectivity was observed in a porphyrin containing a methoxycarbonyl as the electron-withdrawing group, whereas a formyl substituent again resulted in oxidation at the pyrrole unit adjacent to the meso-substituent. Under pinacol-pinacolone conditions, vic-dihydroxy chlorins containing 4-methoxyphenyl or 3,5-dimethoxyphenyl groups at the meso-position showed preferential migration of the ethyl group over the methyl group to give 8-ketochlorins, whereas the diol with an n-heptyl substituent under similar reaction conditions gave both 7- and 8-ketochlorins. In contrast, the diol containing a meso-formyl substituent produced the corresponding 7-ketochlorin exclusively. These results indicate that it is not possible to predict the reactivity of meso-substituted porphyrins in the osmium tetraoxide reaction nor the general substituent migratory aptitudes in the pinacol-pinacolone rearrangement based on simple electronic arguments, most likely because many parameters (e.g., meso-β-pyrrolic steric crowding and long-range electronic effects) ultimately determine the reactivity. The structural assignments of the porphyrin diols and the keto-analogues were confirmed by extensive 1H NMR studies; some of the dihydroxychlorins and ketochlorins were found to display unusual features in their 1H NMR spectra.
- Chen,Medforth,Smith,Alderfer,Dougherty,Pandey
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p. 3930 - 3939
(2007/10/03)
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- THE TOTAL SYNTHESIS OF BILIVERDINS OF BIOLOGICAL INTEREST
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The total synthesis of eight biliverdin isomers was achieved by oxidation of the corresponding 1,19-di-t-butyloxycarbonyl-b-bilenes.One of the biliverdin isomers is mesobiliverdin IXα - a dipropionate bilitriene -, one is a diacetate bilitriene, three iso
- Awruch, Josefina,Frydman, Benjamin
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p. 4137 - 4146
(2007/10/02)
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