Synthesis of meso-Pyrrole-Substituted 22-Oxacorroles by a '' 3+2 '' Approach
DSpace at IIT Bombay
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Title |
Synthesis of meso-Pyrrole-Substituted 22-Oxacorroles by a '' 3+2 '' Approach
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Creator |
KALITA, H
KALITA, D LEE, WZ BELLARE, J RAVIKANTH, M |
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Subject |
ABC-type corroles
biocompatible fluorescent probes pyrrolyl-22-oxacorroles UV Vis spectroscopy CORE-MODIFIED CORROLES 1ST EXAMPLES DIPYRROMETHANES SMARAGDYRINS CONDENSATION |
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Description |
Unsymmetrical 22-oxacorrole containing two aryl groups and one pyrrole group at the meso position was synthesized by condensing one equivalent of 16-oxatripyrrane with one equivalent of meso aryl dipyromethane under mild acid-catalyzed conditions followed by oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). This [3+2] condensation approach was expected to yield meso-free 25-oxasmaragdyrin but unexpectedly afforded unsymmetrical meso-pyrrole-substituted 22-oxacorrole. We demonstrated the versatility of the reaction by synthesizing four new meso-pyrrole-substituted 22-oxacorroles. The reactivity of -position of meso-pyrrole was tested by carrying out various functionalization reactions such as bromination, formylation, and nitration and obtained the functionalized meso-pyrrole-substituted 22-oxacorroles in decent yields. The X-ray structure obtained for one of the functionalized meso-pyrrole substituted 22-oxacorrole revealed that the macrocycle was nearly planar and the meso-pyrrole was in the perpendicular orientation with respect to the macrocyclic plane. The meso-pyrrole-substituted 22-oxacorroles absorb strongly in 400-700nm region with one strong Soret band and four weak Q bands. The 22-oxacorroles are strongly fluorescent and showed emission maxima at approximate to 650nm with decent quantum yields and singlet-state lifetimes. The 22-oxacorroles are redox-active and exhibited three irreversible oxidations and one or two reversible reduction(s). A preliminary biological study indicated that meso-pyrrole corroles are biocompatible.
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Publisher |
WILEY-V C H VERLAG GMBH
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Date |
2014-12-28T12:46:45Z
2014-12-28T12:46:45Z 2014 |
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Type |
Article
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Identifier |
CHEMISTRY-A EUROPEAN JOURNAL, 20(33)10404-10413
0947-6539 1521-3765 http://dx.doi.org/10.1002/chem.201402710 http://dspace.library.iitb.ac.in/jspui/handle/100/16592 |
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Language |
English
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