Volume 2019, Issue 25 p. 4020-4033

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Synthesis of Porphyrinoids, BODIPYs, and (Dipyrrinato)ruthenium(II) Complexes from Prefunctionalized Dipyrromethanes

Benjamin F. Hohlfeld,

Benjamin F. Hohlfeld

orcid.org/0000-0001-8508-2460

Institut für Chemie und Biochemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany

Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34/36, 14195 Berlin, Germany

biolitec research GmbH, Otto-Schott-Str. 15, 07745 Jena, Germany

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Keith J. Flanagan,

Keith J. Flanagan

orcid.org/0000-0003-1656-3177

Medicinal Chemistry, Trinity Translational Medicine Institute, Trinity Centre for Health Sciences, Trinity College Dublin, The University of Dublin, St James's Hospital, 8 Dublin, Ireland

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Nora Kulak,

Nora Kulak

orcid.org/0000-0002-8347-4046

Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34/36, 14195 Berlin, Germany

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Mathias O. Senge,

Mathias O. Senge

orcid.org/0000-0002-7467-1654

Medicinal Chemistry, Trinity Translational Medicine Institute, Trinity Centre for Health Sciences, Trinity College Dublin, The University of Dublin, St James's Hospital, 8 Dublin, Ireland

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Mathias Christmann,

Mathias Christmann

orcid.org/0000-0001-9313-2392

Institut für Chemie und Biochemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany

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Arno Wiehe,

Corresponding Author

Arno Wiehe

orcid.org/0000-0002-6289-7672

Institut für Chemie und Biochemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany

biolitec research GmbH, Otto-Schott-Str. 15, 07745 Jena, Germany

Institut für Chemie und Biochemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany

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Benjamin F. Hohlfeld,

Benjamin F. Hohlfeld

orcid.org/0000-0001-8508-2460

Institut für Chemie und Biochemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany

Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34/36, 14195 Berlin, Germany

biolitec research GmbH, Otto-Schott-Str. 15, 07745 Jena, Germany

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Keith J. Flanagan,

Keith J. Flanagan

orcid.org/0000-0003-1656-3177

Medicinal Chemistry, Trinity Translational Medicine Institute, Trinity Centre for Health Sciences, Trinity College Dublin, The University of Dublin, St James's Hospital, 8 Dublin, Ireland

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Nora Kulak,

Nora Kulak

orcid.org/0000-0002-8347-4046

Institut für Chemie und Biochemie, Freie Universität Berlin, Fabeckstr. 34/36, 14195 Berlin, Germany

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Mathias O. Senge,

Mathias O. Senge

orcid.org/0000-0002-7467-1654

Medicinal Chemistry, Trinity Translational Medicine Institute, Trinity Centre for Health Sciences, Trinity College Dublin, The University of Dublin, St James's Hospital, 8 Dublin, Ireland

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Mathias Christmann,

Mathias Christmann

orcid.org/0000-0001-9313-2392

Institut für Chemie und Biochemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany

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Arno Wiehe,

Corresponding Author

Arno Wiehe

orcid.org/0000-0002-6289-7672

Institut für Chemie und Biochemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany

biolitec research GmbH, Otto-Schott-Str. 15, 07745 Jena, Germany

Institut für Chemie und Biochemie, Freie Universität Berlin, Takustr. 3, 14195 Berlin, Germany

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Dedicated to Professor Hans-Ulrich Reißig on the occasion of his 70th birthday

First published: 29 May 2019

https://doi.org/10.1002/ejoc.201900530

Citations: 15

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Graphical Abstract

The 3,4,5-trifluorophenyl and the 4-fluoro-3-nitrophenyl substituent were evaluated for modifying porphyrins, corroles, BODIPYs, and their dipyrromethane precursors via S_NAr. Specifically, 5-(4-fluoro-3-nitrophenyl)dipyrromethane was efficiently substituted with amines. The prefunctionalized dipyrromethanes served as precursors for meso-substituted BODIPYs, dipyrrins, and their related Ru^II complexes.

Abstract

The introduction of functional groups into the meso-position of dipyrromethanes, boron-dipyrromethenes (BODIPYs) and porphyrinoids, is of fundamental importance in designing such dye systems for material sciences or photomedicine. One route that has proven to be particularly useful in this respect is the nucleophilic aromatic substitution (S_NAr) on porphyrinoids and their precursors carrying electron-withdrawing substituents. To further expand this methodology, the potential of the 4-fluoro-3-nitrophenyl and the 3,4,5-trifluorophenyl moieties for the synthesis of functionalized dipyrromethanes, BODIPYs, and porphyrinoids has been evaluated. The 3,4,5-trifluorophenyl moiety proved not to be applicable in the S_NAr with nucleophiles. The introduction of the 4-fluoro-3-nitrophenyl group, however, allowed fast and efficient S_NAr with various amine nucleophiles. The synthesized 4-amino-3-nitrophenyl-substituted dipyrromethanes were successfully applied in the synthesis BODIPYs and were tested in the synthesis of “trans”-A₂B₂ porphyrins and A₂B corroles. Furthermore, the dipyrromethanes – after oxidation to the dipyrromethenes – were found to be suitable ligands for metal ions giving access to functionalized ruthenium(II) metal complexes.

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Volume2019, Issue25

July 7, 2019

Pages 4020-4033

Synthesis of Porphyrinoids, BODIPYs, and (Dipyrrinato)ruthenium(II) Complexes from Prefunctionalized Dipyrromethanes

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Synthesis of Porphyrinoids, BODIPYs, and (Dipyrrinato)ruthenium(II) Complexes from Prefunctionalized Dipyrromethanes

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