A NOVEL ANION-BINDING CHIRAL RECEPTOR-BASED ON A METALLOPORPHYRIN WITH MOLECULAR ASYMMETRY - HIGHLY ENANTIOSELECTIVE RECOGNITION OF AMINO-ACID DERIVATIVES
A NOVEL ANION-BINDING CHIRAL RECEPTOR-BASED ON A METALLOPORPHYRIN WITH MOLECULAR ASYMMETRY - HIGHLY ENANTIOSELECTIVE RECOGNITION OF AMINO-ACID DERIVATIVES
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DOI：
10.1021/ja00083a019
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发表时间：
1994-02-23
影响因子：
15
通讯作者：
INOUE, S
中科院分区：
文献类型：
--
作者：
KONISHI, K;YAHARA, K;INOUE, S
以具有对映异构体的mesoporphyrin II为原料，合成了一种手性锌束缚的N-甲基化卟啉（3c），该卟啉（3c）具有分子不对称性，其特征在于一个金属原子与羧酸根阴离子结合，一个刚性的对苯二甲撑带通过两个酰胺键锚定，并用HPLC对3c的光学异构体进行了拆分。通过使用3c作为手性受体，实现了对N-苄氧羰基，叔丁氧羰基，3，5-二硝基苯甲酰基和乙酰基氨基酸的羧酸根阴离子的高度对映选择性结合。红外光谱和核磁共振研究表明，受体与底物之间的氢键相互作用在手性识别中起着至关重要的作用。
A chiral zinc strapped N-methylated porphyrin (3c) with molecular asymmetry, featuring a metal atom to bind a carboxylate anion and a rigid p-xylylene strap anchored via two amide linkages, was synthesized from mesoporphyrin II with enantiotopic fades, and the optical isomers of 3c were resolved by HPLC. By using 3c as a chiral receptor, the highly enantioselective binding was achieved for the carboxylate anions of N-benzyloxycarbonyl, tert-butoxycarbonyl, 3,5-dinitrobenzoyl, and acetyl amino acids. IR and NMR studies demonstrated the crucial role of the hydrogen bonding interaction between the receptor and substrates in the chiral recognition.