Synthesis of New Amino-Functionalized Porphyrins:Preliminary Study of Their Organophotocatalytic Activity
The design, synthesis, and initial study of amino-functionalized porphyrins as a new class of bifunctional catalysts for asymmetric organophotocatalysis is described. Two new types of amine–porphyrin hybrids derived from 5,10,15,20-tetraphenylporphyrin (TPPH<sub>2</sub>), in which a cycl...
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MDPI AG
2023-02-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/28/4/1997 |
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| author | Pol Torres Marian Guillén Marc Escribà Joaquim Crusats Albert Moyano |
| author_facet | Pol Torres Marian Guillén Marc Escribà Joaquim Crusats Albert Moyano |
| author_sort | Pol Torres |
| collection | DOAJ |
| description | The design, synthesis, and initial study of amino-functionalized porphyrins as a new class of bifunctional catalysts for asymmetric organophotocatalysis is described. Two new types of amine–porphyrin hybrids derived from 5,10,15,20-tetraphenylporphyrin (TPPH<sub>2</sub>), in which a cyclic secondary amine moiety is covalently linked either to a β-pyrrolic position (Type A) or to the <i>p</i>-position of one of the <i>meso</i> phenyl groups (Type B), were prepared by condensation, reductive amination, or amidation reactions from the suitable porphyrins (either formyl or methanamine derivatives) with readily available chiral amines. A preliminary study of the possible use of Type A amine–porphyrin hybrids as asymmetric, bifunctional organophotocatalysts was performed using the chiral, imidazolidinone-catalyzed Diels–Alder cycloaddition between cyclopentadiene 28 and <i>trans</i>-cinnamaldehyde 29 as a benchmark reaction. The yield and the stereochemical outcome of this process, obtained under purely organocatalytic conditions, under dual organophocatalysis, and under bifunctional organophotocatalysis, were compared. |
| first_indexed | 2024-03-11T08:21:29Z |
| format | Article |
| id | doaj.art-de4c7995eb5040c5af0569666c62dbbf |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-11T08:21:29Z |
| publishDate | 2023-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-de4c7995eb5040c5af0569666c62dbbf2023-11-16T22:26:07ZengMDPI AGMolecules1420-30492023-02-01284199710.3390/molecules28041997Synthesis of New Amino-Functionalized Porphyrins:Preliminary Study of Their Organophotocatalytic ActivityPol Torres0Marian Guillén1Marc Escribà2Joaquim Crusats3Albert Moyano4Section of Organic Chemistry, Department of Inorganic and Organic Chemistry, Faculty of Chemistry, University of Barcelona, C. de Martí i Franquès 1-11, 08028 Barcelona, SpainSection of Organic Chemistry, Department of Inorganic and Organic Chemistry, Faculty of Chemistry, University of Barcelona, C. de Martí i Franquès 1-11, 08028 Barcelona, SpainSection of Organic Chemistry, Department of Inorganic and Organic Chemistry, Faculty of Chemistry, University of Barcelona, C. de Martí i Franquès 1-11, 08028 Barcelona, SpainSection of Organic Chemistry, Department of Inorganic and Organic Chemistry, Faculty of Chemistry, University of Barcelona, C. de Martí i Franquès 1-11, 08028 Barcelona, SpainSection of Organic Chemistry, Department of Inorganic and Organic Chemistry, Faculty of Chemistry, University of Barcelona, C. de Martí i Franquès 1-11, 08028 Barcelona, SpainThe design, synthesis, and initial study of amino-functionalized porphyrins as a new class of bifunctional catalysts for asymmetric organophotocatalysis is described. Two new types of amine–porphyrin hybrids derived from 5,10,15,20-tetraphenylporphyrin (TPPH<sub>2</sub>), in which a cyclic secondary amine moiety is covalently linked either to a β-pyrrolic position (Type A) or to the <i>p</i>-position of one of the <i>meso</i> phenyl groups (Type B), were prepared by condensation, reductive amination, or amidation reactions from the suitable porphyrins (either formyl or methanamine derivatives) with readily available chiral amines. A preliminary study of the possible use of Type A amine–porphyrin hybrids as asymmetric, bifunctional organophotocatalysts was performed using the chiral, imidazolidinone-catalyzed Diels–Alder cycloaddition between cyclopentadiene 28 and <i>trans</i>-cinnamaldehyde 29 as a benchmark reaction. The yield and the stereochemical outcome of this process, obtained under purely organocatalytic conditions, under dual organophocatalysis, and under bifunctional organophotocatalysis, were compared.https://www.mdpi.com/1420-3049/28/4/1997asymmetric catalysisDiels–Alder reactionimidazolidin-4-onesorganocatalysisphotocatalysisporphyrins |
| spellingShingle | Pol Torres Marian Guillén Marc Escribà Joaquim Crusats Albert Moyano Synthesis of New Amino-Functionalized Porphyrins:Preliminary Study of Their Organophotocatalytic Activity Molecules asymmetric catalysis Diels–Alder reaction imidazolidin-4-ones organocatalysis photocatalysis porphyrins |
| title | Synthesis of New Amino-Functionalized Porphyrins:Preliminary Study of Their Organophotocatalytic Activity |
| title_full | Synthesis of New Amino-Functionalized Porphyrins:Preliminary Study of Their Organophotocatalytic Activity |
| title_fullStr | Synthesis of New Amino-Functionalized Porphyrins:Preliminary Study of Their Organophotocatalytic Activity |
| title_full_unstemmed | Synthesis of New Amino-Functionalized Porphyrins:Preliminary Study of Their Organophotocatalytic Activity |
| title_short | Synthesis of New Amino-Functionalized Porphyrins:Preliminary Study of Their Organophotocatalytic Activity |
| title_sort | synthesis of new amino functionalized porphyrins preliminary study of their organophotocatalytic activity |
| topic | asymmetric catalysis Diels–Alder reaction imidazolidin-4-ones organocatalysis photocatalysis porphyrins |
| url | https://www.mdpi.com/1420-3049/28/4/1997 |
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