Callaghan Susan, Flanagan Keith J, O'Brien John E, Senge Mathias O
School of Chemistry Trinity College Dublin The University of Dublin Trinity Biomedical Sciences Institute 152-160 Pearse Street Dublin 2 Ireland.
Institute for Advanced Study (TUM-IAS) Technische Universität München Lichtenberg-Str. 2a 85748 Garching Germany.
European J Org Chem. 2020 May 14;2020(18):2735-2744. doi: 10.1002/ejoc.202000283. Epub 2020 Apr 20.
The syntheses of short-chained anthracene-strapped porphyrins and their Zn(II)complexes are reported. The key synthetic step is a [2+2] condensation between a dipyrromethane and an anthracene bisaldehyde, 2,2'-((anthracene-9,10-diylbis(methylene))bis(oxy))dibenzaldehyde. Following exposure to white light, self-sensitized singlet oxygen and the anthracene moieties underwent [4+2] cycloaddition reactions to yield the corresponding endoperoxides. H NMR studies demonstrate that the endoperoxide readily formed in [D]chloroform and decayed at 85 °C. X-ray crystallography and absorption spectroscopy were used to confirm macrocyclic distortion in the parent strapped porphyrins and endoperoxides. Additionally, X-ray crystallography indicated that endoperoxide formation occurred exclusively on the outside face of the anthracene moiety.
本文报道了短链蒽桥连卟啉及其锌（II）配合物的合成。关键合成步骤是二吡咯甲烷与蒽双醛2,2'-((蒽-9,10-二亚甲基)双(氧基))二苯甲醛之间的[2+2]缩合反应。在白光照射下，自敏化单线态氧与蒽部分发生[4+2]环加成反应，生成相应的内过氧化物。1H NMR研究表明，内过氧化物在[D]氯仿中容易形成，并在85°C下分解。利用X射线晶体学和吸收光谱法证实了母体桥连卟啉和内过氧化物中的大环畸变。此外，X射线晶体学表明，内过氧化物的形成仅发生在蒽部分的外表面。
