Kobayashi Toi, Kumagai Naoya
Graduate School of Pharmaceutical Sciences, Keio University, 1-5-30 Shibakoen, Minato-ku, Tokyo, 105-8512, Japan.
Institute of Microbial Chemistry, 3-14-23 Kamiosaki, Shinagawa-ku, Tokyo, 141-0021, Japan.
Angew Chem Int Ed Engl. 2023 Aug 7;62(32):e202307896. doi: 10.1002/anie.202307896. Epub 2023 Jul 3.
A new 15-membered-macrocyclic molecular entity, oxa-TriQuinoline (o-TQ), was designed and synthesized. In o-TQ, three oxygen atoms were joined onto three quinoline units at the 2- and 8-positions in a head-to-tail fashion by three-fold S Ar reactions, giving rise to the characteristic N O aza-oxa-crown architecture. o-TQ can serve as a new tridentate nitrogen ligand to capture a Cu cation and adopt a bowl shape, before supramolecular complexation with corannulene and [12]cycloparaphenylene (CPP) occurs through π-π and CH-π interactions. In the presence of the Cu cation, the non-emissive o-TQ becomes a highly emissive material in the solid state, whereby the emission wavelengths depend on the ancillary ligand on the Cu cation. The o-TQ/Cu complex is able to promote carbene catalysis to provide a range of enamines with a gem-difluorinated terminus.
设计并合成了一种新的15元大环分子实体，即氧杂三喹啉（o-TQ）。在o-TQ中，三个氧原子通过三次S Ar反应以头对尾的方式连接到三个喹啉单元的2位和8位，形成了独特的N O氮杂氧杂冠醚结构。o-TQ可以作为一种新的三齿氮配体捕获铜阳离子，并呈碗状，然后通过π-π和CH-π相互作用与碗烯和[12]环对亚苯基（CPP）发生超分子络合。在铜阳离子存在下，不发光的o-TQ在固态下变成高发光材料，其发射波长取决于铜阳离子上的辅助配体。o-TQ/Cu络合物能够促进卡宾催化，提供一系列具有偕二氟端基的烯胺。
