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Brückner C, Götz DC, Fox SP, et al. Helimeric porphyrinoids: stereostructure and chiral resolution of meso-tetraarylmorpholinochlorins. J Am Chem Soc. 2011;133(22):8740-52doi: 10.1021/ja202451t.
Brückner, C., Götz, D. C., Fox, S. P., Ryppa, C., McCarthy, J. R., Bruhn, T., Akhigbe, J., Banerjee, S., Daddario, P., Daniell, H. W., Zeller, M., Boyle, R. W., & Bringmann, G. (2011). Helimeric porphyrinoids: stereostructure and chiral resolution of meso-tetraarylmorpholinochlorins. Journal of the American Chemical Society, 133(22), 8740-52. https://doi.org/10.1021/ja202451t
Brückner, Christian, et al. "Helimeric porphyrinoids: stereostructure and chiral resolution of meso-tetraarylmorpholinochlorins." Journal of the American Chemical Society vol. 133,22 (2011): 8740-52. doi: https://doi.org/10.1021/ja202451t
Brückner C, Götz DC, Fox SP, Ryppa C, McCarthy JR, Bruhn T, Akhigbe J, Banerjee S, Daddario P, Daniell HW, Zeller M, Boyle RW, Bringmann G. Helimeric porphyrinoids: stereostructure and chiral resolution of meso-tetraarylmorpholinochlorins. J Am Chem Soc. 2011 Jun 08;133(22):8740-52. doi: 10.1021/ja202451t. Epub 2011 May 13. PMID: 21534626.
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J Am Chem Soc. 2011 Jun 08;133(22):8740-52. doi: 10.1021/ja202451t. Epub 2011 May 13.

Helimeric porphyrinoids: stereostructure and chiral resolution of meso-tetraarylmorpholinochlorins.

Journal of the American Chemical Society

Christian Brückner, Daniel C G Götz, Simon P Fox, Claudia Ryppa, Jason R McCarthy, Torsten Bruhn, Joshua Akhigbe, Subhadeep Banerjee, Pedro Daddario, Heather W Daniell, Matthias Zeller, Ross W Boyle, Gerhard Bringmann

Affiliations

  1. Department of Chemistry, University of Connecticut, Storrs, Connecticut 06269-3060, USA. [email protected]

PMID: 21534626 DOI: 10.1021/ja202451t

Abstract

The synthesis and chiral resolution of free-base and Ni(II) complexes of a number of derivatives of meso-tetraphenylmorpholinochlorins, with and without direct β-carbon-to-o-phenyl linkages to the flanking phenyl groups, is described. The morpholinochlorins, a class of stable chlorin analogues, were synthesized in two to three steps from meso-tetraphenylporphyrin. The conformations and the relative stereostructures of a variety of free-base and Ni(II) complexes of these morpholinochlorins were elucidated by X-ray diffractometry. Steric and stereoelectronic arguments explain the relative stereoarray of the morpholino-substituents, which differ in the free-base and Ni(II) complexes, and in the monoalkoxy, β-carbon-to-o-phenyl linked morpholinochlorins, and the dialkoxy derivatives. The Ni(II) complexes were all found to be severely ruffled whereas the free-base chromophores are more planar. As a result of the helimeric distortion of their porphyrinoid chromophores, the ruffled macrocycles possess a stable inherent element of chirality. Most significantly, resolution of the racemic mixtures was achieved, both by classical methods via diastereomers and by HPLC on a chiral phase. Full CD spectra were recorded and modeled using quantum-chemical computational methods, permitting, for the first time, an assignment of the absolute configurations of the chromophores. The report expands the range of known pyrrole-modified porphyrins. Beyond this, it introduces large chiral porphyrinoid π-systems that exist in the form of two enantiomeric, stereochemically stable helimers that can be resolved. This forms the basis for possible future applications, for example, in molecular-recognition systems or in materials with chiroptic properties.

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