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Li R, Lammer AD, Ferrence GM, et al. Synthesis, structural characterization, aromatic characteristics, and metalation of neo-confused porphyrins, a newly discovered class of porphyrin isomers. J Org Chem. 2014;79(9):4078-93doi: 10.1021/jo500580e.
Li, R., Lammer, A. D., Ferrence, G. M., & Lash, T. D. (2014). Synthesis, structural characterization, aromatic characteristics, and metalation of neo-confused porphyrins, a newly discovered class of porphyrin isomers. The Journal of organic chemistry, 79(9), 4078-93. https://doi.org/10.1021/jo500580e
Li, Ruoshi, et al. "Synthesis, structural characterization, aromatic characteristics, and metalation of neo-confused porphyrins, a newly discovered class of porphyrin isomers." The Journal of organic chemistry vol. 79,9 (2014): 4078-93. doi: https://doi.org/10.1021/jo500580e
Li R, Lammer AD, Ferrence GM, Lash TD. Synthesis, structural characterization, aromatic characteristics, and metalation of neo-confused porphyrins, a newly discovered class of porphyrin isomers. J Org Chem. 2014 May 02;79(9):4078-93. doi: 10.1021/jo500580e. Epub 2014 Apr 18. PMID: 24697282.
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J Org Chem. 2014 May 02;79(9):4078-93. doi: 10.1021/jo500580e. Epub 2014 Apr 18.

Synthesis, structural characterization, aromatic characteristics, and metalation of neo-confused porphyrins, a newly discovered class of porphyrin isomers.

The Journal of organic chemistry

Ruoshi Li, Aaron D Lammer, Gregory M Ferrence, Timothy D Lash

Affiliations

  1. Department of Chemistry, Illinois State University , Normal, Illinois 61790-4160, United States.

PMID: 24697282 DOI: 10.1021/jo500580e

Abstract

Neo-confused porphyrins represent a unique family of porphyrin isomers that retain overall aromatic characteristics by virtue of a 17-atom 18π electron delocalization pathway. These porphyrin analogues have a pyrrolic subunit linked in a 1,3-fashion so that a nitrogen atom is directly connected to a meso-bridging carbon. Pyrrole-3-carbaldehydes were shown to react with sodium hydride and 5-acetoxymethylpyrrole-2-carbaldehydes in DMF to give the crucial neo-confused dipyrrolic dialdehyde intermediates. MacDonald "2 + 2" condensation of the dialdehydes with a dipyrrylmethane afforded a dihydroporphyrinoid, and subsequent oxidation with 0.2% aqueous ferric chloride generated a series of fully conjugated neo-confused porphyrins. Unusual dihydroporphyrin byproducts were also identified. Reaction of neo-confused porphyrins with nickel(II) or palladium(II) acetate in refluxing acetonitrile gave excellent yields of the corresponding organometallic derivatives. Proton NMR spectroscopy demonstrates that the diatropic character of this system is diminished compared to regular porphyrins, although neo-confused porphyrins retain porphyrin-like UV-vis spectra. Protonation led to the sequential formation of mono- and dicationic species. Proton NMR spectra for the dications showed the presence of enhanced diamagnetic ring currents.

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