Synthesis of Phenaliporphyrin, a PAH-Porphyrin Hybrid, from an Acenaphthene-Fused Cyclopropane Dialdehyde
Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide Phenaliporphyrin, a new aromatic benziporphyrin derivative, has been synthesized from an annulated cyclopropane dialdehyde intermediate. Corey-Chaykovsky cyclopropanation of dimethyl acenaphthylene-1,2-dicarboxylate gave a cyclopropane diester, and this was converted to the corresponding bis-Weinreb amide. Reduction with lithium aluminum hydride afforded an unstable dialdehyde and subsequent acid-catalyzed condensation with a tripyrrane dicarboxylic acid, followed by oxidation with aqueous ferric chloride, gave the targeted porphyrinoid system. This involves ring expansion of the acenaphthylene precursor to generate the phenalene unit. Phenaliporphyrin exhibits a porphyrin-like UV–vis spectrum with a Soret band at 443 nm and a relatively intense Q-band at 601 nm. The proton NMR spectrum demonstrated that the system has a strong diamagnetic ring current, and the external meso -protons showed up downfield at 9.64 and 9.34 ppm while the internal C–H appeared upfield at −6.48 ppm. Although DFT calculations show that the phenalene ring is twisted to relieve steric interactions, single crystal X-ray diffraction analysis indicated that the macrocycle is nearly planar. The discrepancy was attributed to crystal packing forces and a distorted conformation is likely to be favored in solution. The aromatic properties for phenaliporphyrin were confirmed by nucleus independent chemical shift (NICS) calculations and anisotropy of induced current density plots.
Source: The Journal of Organic Chemistry
Authors: Sunday Oladapo Jacob, Emily D. Harris, Melissa A. Mathius, Deyaa I. AbuSalim, Gregory M. Ferrence, Timothy D. Lash
Institutions: Illinois State University, Rowan University
Language: English
Subfield: Materials Chemistry
Field: Materials Science
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Awards: G2427078641, MRI: Acquisition of a High Resolution LC-MS/MS System for Research and Education, MRI: Track 1 Acquisition of a Cu micro-source and High-Performance Area Detector Equipped Single Crystal X-ray Diffractometer for Research and Teaching, MRI: Acquisition of 400 MHz NMRs for Research and Education, RUI: New Porphyrinoid Architectures with Extended Conjugation Pathways, G6035840920
OpenAlex ID: W4416845330