Investigating the diastereoselective synthesis of a macrocycle under Curtin-Hammett control
Investigating the diastereoselective synthesis of a macrocycle under Curtin-Hammett control
复制标题
DOI：
10.1039/d3sc05715a
复制
发表时间：
2024-03-05
期刊：
影响因子：
8.4
通讯作者：
Barendt，Timothy A.
中科院分区：
文献类型：
--
作者：
Yeung，Angus;Zwijnenburg，Martijn A.;Barendt，Timothy A.
这一工作为手性大环化合物的立体选择性合成提供了新的思路。手性大环化合物具有π共轭结构，在识别、传感和光电子学等领域具有重要的应用价值。首次，我们使用Curtin-Hammett原理来研究手性大环化反应，揭示了超分子π-π相互作用的潜力，以指导动态动力学拆分的结果，有利于相反的大环产物，预期在可逆的，可控的条件下。具体而言，动态外消旋的二萘嵌苯二酰亚胺染料（1：1 P：M）与对映体纯的（S）-1，1 ′-联-2-萘酚基团（P-BINOL）结合以形成两种非对映体大环产物，即纯手性大环（PP）和杂手性物质（PM）。 我们发现PM大环（dr = 4：1）具有显著的选择性，这是通过在大环化反应期间P-BINOL π-供体和M-PDI π-受体之间的分子内芳香族非共价相互作用的动力学模板来合理化的。
This work sheds new light on the stereoselective synthesis of chiral macrocycles containing twisted aromatic units, valuable π-conjugated materials for recognition, sensing, and optoelectronics. For the first time, we use the Curtin–Hammett principle to investigate a chiral macrocyclisation reaction, revealing the potential for supramolecular π–π interactions to direct the outcome of a dynamic kinetic resolution, favouring the opposite macrocyclic product to that expected under reversible, thermodynamically controlled conditions. Specifically, a dynamic, racemic perylene diimide dye (1 : 1 P : M) is strapped with an enantiopure (S)-1,1′-bi-2-naphthol group (P-BINOL) to form two diastereomeric macrocyclic products, the homochiral macrocycle (PP) and the heterochiral species (PM). We find there is notable selectivity for the PM macrocycle (dr = 4 : 1), which is rationalised by kinetic templation from intramolecular aromatic non-covalent interactions between the P-BINOL π-donor and the M-PDI π-acceptor during the macrocyclisation reaction.