Synthesis of cyclodextrin derivatives for enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate
Synthesis of cyclodextrin derivatives for enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylate
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DOI：
10.1038/s41596-022-00722-6
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发表时间：
2022-08
期刊：
影响因子：
14.8
通讯作者：
Xueqin Wei;Jie Ji;Yongxin Nie;Liangjian Tang;M. Rao;Xiaoqian Wang;Wanhua Wu;Dan Su;Zhihui Zhong;Cheng Yang
中科院分区：
文献类型：
--
作者：
Xueqin Wei;Jie Ji;Yongxin Nie;Liangjian Tang;M. Rao;Xiaoqian Wang;Wanhua Wu;Dan Su;Zhihui Zhong;Cheng Yang
光化学方法越来越多地用于有机合成。它们特别适用于制备许多不易通过热或酶反应获得的化合物。近年来，超分子策略已被证明是非常有前途的操纵手性光反应的立体化学的结果，通过在基态和激发态相对较强和持久的非共价相互作用。在众多的手性光化学反应中，2-蒽甲酸（AC）的光环化二聚反应是研究最多的超分子手性光反应，已成为评价超分子光手性的基准反应。环糊精（CD）衍生物是最早和最广泛应用于光催化反应的手性主体。本文以CD介导的AC光环化二聚反应为例，介绍了超分子手性光反应的操作过程。该方案包括以下内容：（i）β-CD衍生物的制备、纯化和表征;（ii）AC与β-CD衍生物之间主客体包结行为的研究方法;（iii）不同溶剂和温度条件下的光化学反应操作流程;（iv）手性高效液相色谱（HPLC）分析产物分布和对映体选择性。该方案通过使用β-CD衍生物的合成和环境因素的操作的代表性例子进行介绍，这些环境因素在AC的光环化二聚中提供了优异的区域选择性和对映选择性。β-CD衍生物的合成和纯化需要3-5天的工作。AC与β-CD衍生物的光照射可在1h内完成。产物分析需要5小时。
Photochemical methods are increasingly being used in organic synthesis. They are especially useful for preparing many compounds that are not readily accessible through thermal or enzymatic reactions. The supramolecular strategy has proved highly promising in recent years for manipulating the stereochemical outcome of chiral photoreactions through relatively strong and long-lasting noncovalent interactions in both ground and excited states. Among the numerous chiral photochemical reactions, photocyclodimerization of 2-anthracenecarboxylate (AC) is the most comprehensively studied supramolecular chiral photoreaction and has essentially become a benchmark reaction for evaluating supramolecular photochirogenesis. Cyclodextrin (CD) derivatives were the earliest and are the most widely applied chiral host for mediating photoreactions. Herein, we use CD-mediated photocyclodimerization of AC as an example to introduce the operation process of supramolecular chiral photoreactions. The protocol includes the following contents: (i) the preparation, purification and characterization of β-CD derivatives; (ii) methods for investigating the host–guest inclusion behavior between AC and β-CD derivatives; (iii) the photochemical reaction operation flow under different solvent and temperature conditions; (iv) chiral high-performance liquid chromatography (HPLC) analyses of the product distribution and enantioselectivity. The protocol is introduced by using representative examples of the synthesis of β-CD derivatives and the manipulation of environmental factors that give excellent regio- and enantioselectivities in the photocyclodimerization of AC. The synthesis and purification of β-CD derivatives require 3–5 d of work. The photoirradiation of AC with β-CD derivatives can be done within 1 h. The product analysis requires 5 h.