Synthesis of functionalized porphyrins as oxygen ligand receptors.
Synthesis of functionalized porphyrins as oxygen ligand receptors.
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作为氧配体受体的功能化卟啉的合成。
DOI：
10.1021/jo026850
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发表时间：
2003
期刊：
影响因子：
--
通讯作者：
S. Kitagawa
中科院分区：
文献类型：
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作者：
K. Wada;T. Mizutani;S. Kitagawa
设计和合成了亲氧性的合成受体，目的是构建一个预先组织的酚类和碳水化合物的互补结合部位。我们探索了三种识别苯酚的策略：(1)Lewis酸/Lewis碱组合作为氢键的供体和受体，(2)Lewis碱/pi-pi堆积，同时针对酚的羟基和芳香族部分，以及(3)轴向羟基配体在铝卟啉的三价亲氧金属中心上交换。对于酸性酚的识别，最有希望的识别基序是Lewis碱/pi-pi堆积，它可以通过氢键和pi-pi堆积作用与苯酚结合。在25℃的CHCl(3)介质中，[5-(8-Quinolyl)-10，15，20-triphenylporphyrinato]zinc与对-硝基苯酚的结合常数为540M(-)(1)。为了识别碳水化合物，我们设计了具有8-喹啉基团和邻甲基甲氧基苯基的金属卟啉受体，其中这些Lewis碱性部分作为糖苷羟基的协同氢键中心。在15℃的CHCl(3)中，受体与β-辛基葡萄糖苷的结合常数为7.35×10(4)M(-)(1)，表明在受体和客体之间形成高度有序的氢键网络的重要性。这些结合特征对亲氧性人工受体的合理设计具有重要意义。
Oxophilic synthetic receptors were designed and synthesized using a porphyrin scaffold, with the aim of constructing a preorganized complementary binding site for phenols and carbohydrates. We pursued three strategies for phenol recognition: (1) Lewis acid/Lewis base combinations serving as a hydrogen bond donor and acceptor for the OH group, (2) Lewis base/pi-pi stacking, targeting both the OH group and the aromatic moiety of phenols, and (3) exchange of the axial hydroxyl ligand on a trivalent and oxophilic metal center of aluminum porphyrin. For the recognition of acidic phenols, the most promising recognition motif was Lewis base/pi-pi stacking, which can bind to phenols with a hydrogen bond and pi-pi stacking interactions. [5-(8-Quinolyl)-10,15,20-triphenylporphyrinato]zinc binds to p-nitrophenol with a binding constant of 540 M(-)(1) in CHCl(3) at 25 degrees C. For carbohydrate recognition, we designed the metalloporphyrin receptor having 8-quinolyl groups and o-carbomethoxymethoxyphenyl groups, where these Lewis basic parts serve as the cooperative hydrogen bonding sites for the hydroxyl groups of glucoside. The receptor binds to beta-octyl glucoside with a binding constant of 7.35 x 10(4) M(-)(1) in CHCl(3) at 15 degrees C, demonstrating importance of formation of a highly ordered hydrogen bonding network between the receptor and the guest. These binding features have significant implications for the rational design of oxophilic artificial receptors.