|
Z. Naturforsch. 2014,
69b, 889 – 898
doi:10.5560/ZNB.2014-4100
Synthesis of Diazepine-fused Porphyrinoids and Annulated Porphyrin Arrays
1 School of Chemistry, SFI Tetrapyrrole Laboratory, Trinity Biomedical Sciences Institute, 152–160 Pearse Street, Trinity College Dublin, Dublin 2, Ireland
2 Aix Marseille Université, CNRS, UMR iSm2 7313, F-13397 Marseille, France
3 Medicinal Chemistry, Institute of Molecular Medicine, Trinity Centre for Health Sciences, Trinity College Dublin, St James's Hospital, Dublin 8, Ireland
Reprint requests to Prof. Dr. M. O. Senge. Fax: #353-1-896-8537. E-mail:
sengem@tcd.ie
Received May 15, 2014 / published online August 12, 2014
Porphyrins with exocyclic rings allow for significant modulation of the photochemical properties of the macrocycle via modulation of the aromatic system through electronic and conformational effects. Here we sought to generate such porphyrinoids via a stepwise strategy involving two cycloaddition steps, the first improving the synthesis of a relatively unstable dehydropurpurin intermediate which ring opens to form a key 1,5-diketone species. A library of a new class of porphyrinoids, namely diazepine-fused porphyrinoids was synthesized via condensation methods from these 1,5-diketone precursors in yields of 8%–49%. Cycloaddition methodologies were also applied to bisporphyrins, and their reactivities were investigated.
Key words: Porphyrinoids, Cycloaddition, Diazepine, 1,5-Diketones