Ishida Shin-Ichiro, Soya Takanori, Osuka Atsuhiro
Department of Chemistry, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwakecho, Kyoto, 606-8502, Japan.
Angew Chem Int Ed Engl. 2018 Oct 8;57(41):13640-13643. doi: 10.1002/anie.201808513. Epub 2018 Sep 11.
5,20-Dibenzoyl [28]hexaphyrin(1.1.1.1.1.1) was synthesized as the first hexaphyrin bearing meso-aroyl substituents. The meso-dibenzoyl substituents are hydrogen-bonded with the pyrrolic protons to stabilize an antiaromatic dumbbell conformer. Core metalation of this hexaphyrin with Au afforded rectangular and aromatic [26]hexaphyrin bis-Au complexes, the major isomer of which was reduced with NaBH to give its antiaromatic 28π bis-Au complex. This complex allowed facile peripheral metalation with B owing to the peripheral benzoyl substituents.
5,20-二苯甲酰基[28]六卟啉(1.1.1.1.1.1)作为首个带有中位芳酰基取代基的六卟啉被合成出来。中位二苯甲酰基取代基与吡咯质子形成氢键，以稳定一种反芳香哑铃状构象体。该六卟啉与金进行核心金属化反应，得到矩形且具芳香性的[26]六卟啉双金配合物，其中主要异构体用硼氢化钠还原，得到其反芳香性的28π双金配合物。由于存在外围苯甲酰基取代基，该配合物使得与硼进行外围金属化反应变得容易。
