Synthetic Pathway to <i>trans</i> -A <sub>2</sub> B <sub>2</sub> -Porphyrins: From Oxime-Substituted Dipyrromethanes to Functionalized Macrocycles
An unprecedented approach to <i>trans</i>-A<sub>2</sub>B<sub>2</sub>-porphyrins from α-oxime-functionalized dipyrromethanes has been disclosed. Initially aimed at BODIPY synthesis, the process serendipitously yielded porphyrins with photophysical properties suitable for use as photosensitizers in photodynamic therapy (PDT), as mirrored by its Φ<sub>Δ</sub> values, which ranged from 66% to 86%. This unexpected discovery paves the way for innovative synthetic approaches to macrocycles via DDQ-mediated metal-free C(sp<sup>3</sup>)-C(sp<sup>2</sup>) cross-coupling reactions. The synthesis under batch reaction conditions was successfully transposed to the more sustainable continuous-flow synthesis. Furthermore, <i>meso</i>-oxime-functionalized <i>trans</i>-A<sub>2</sub>B<sub>2</sub>-porphyrins were also obtained via the classic [2 + 2]-type reaction between <i>meso</i>-oxime-functionalized dipyrromethanes and aldehydes.
Authors
- J. Sérgio Seixas de Melo (ORCID: https://orcid.org/0000-0001-9708-5079)
- Marta Piñeiro (ORCID: https://orcid.org/0000-0002-7460-3758)
- Susana M. M. Lopes (ORCID: https://orcid.org/0000-0002-1580-5667)
- João C. S. Simões (ORCID: https://orcid.org/0000-0001-9755-0129)
- Ana Clara B. Rodrigues (ORCID: https://orcid.org/0000-0002-5128-0204)
- Teresa M. V. D. Pinho e Melo (ORCID: https://orcid.org/0000-0003-3256-4954)
- Bruna D. P. Costa (ORCID: https://orcid.org/0000-0002-3995-0164)
Institutions
- University of Coimbra (PT)
Publication Details
- Journal
- The Journal of Organic Chemistry
- Published
- 2025-10-31
- DOI
- https://doi.org/10.1021/acs.joc.5c01907
- Primary Topic
- Porphyrin and Phthalocyanine Chemistry
- Type
- article
- Field-Weighted Citation Impact
- 0.00