School of Chemistry, Chair of Organic Chemistry, Trinity Biomedical Sciences Institute, Trinity College Dublin, The University of Dublin, 152-160 Pearse Street, D02R590, Dublin, Ireland.
School of Chemistry, Trinity College Dublin, The University of Dublin, Dublin 2, Ireland.
Angew Chem Int Ed Engl. 2023 Jun 26;62(26):e202302771. doi: 10.1002/anie.202302771. Epub 2023 Apr 25.
We report a two-step approach to obtain synthetically versatile bicyclo[1.1.1]pentane (BCP) derivatives using Grignard reagents. This method allows the incorporation of BCP units in tetrapyrrolic macrocycles and the synthesis of a new class of calix[4]pyrrole analogues by replacing two bridging methylene groups with two BCP units. In addition, a doubly N-confused system was also formed in the presence of electron-withdrawing substituents at the BCP bridgeheads. The pyrrole rings in BCP containing macrocycles exist in 1,3-alternate or αβαβ conformations, as observed from single-crystal X-ray diffraction analyses and 2D NMR spectroscopy.
我们报告了一种两步法，使用格氏试剂来获得具有合成多功能性的双环[1.1.1]戊烷（BCP）衍生物。该方法允许在四吡咯大环中引入 BCP 单元，并通过用两个 BCP 单元取代两个桥接亚甲基来合成一类新的杯[4]吡咯类似物。此外，在 BCP 桥头上存在吸电子取代基的情况下，还形成了双 N-混淆系统。从单晶 X 射线衍射分析和二维 NMR 光谱中可以看出，含 BCP 的大环中的吡咯环存在 1,3-交替或αβαβ构象。
