Department of Chemistry and Biochemistry, Brigham Young University, Provo, UT 84602, USA.
Org Biomol Chem. 2012 Sep 28;10(36):7392-401. doi: 10.1039/c2ob25613d.
Resorcinarene-based deep cavitands alanine methyl resorcinarene acid (AMA), alanine undecyl resorcinarene acid (AUA) and glycine undecyl resorcinarene acid (GUA), which contain chiral amino acids, have been synthesized. The upper rim of the resorcinarene host is elongated with four identical substituents topped with alanine and glycine groups. The structures of the new resorcinarenes were elucidated by nuclear magnetic resonance (NMR), mass spectrometry (MS) and the sustained off-resonance irradiation collision induced dissociation (SORI-CID) technique in FTICR-MS. These studies revealed that eight water molecules associate to the cavitand, two for each alanine group. The alanine substituent groups are proposed to form a kite-like structure around the resorcinarene scaffold. The binding of AMA, AUA, and GUA with chiral R- and S-methyl benzyl amines was studied by (1)H NMR titration, and compared to that of a binary L-tartaric acid and the monoacid phthalyl alanine (PA). The results show that these compounds interact with amine guests; however, with four carboxylic acid groups, they bind several amine molecules strongly while the binary L-tartaric acid only binds one amine guest strongly. The simple compound PA, which contains one carboxylic group, shows weak binding to the amines. The (1)H NMR titration of AUA with primary, secondary, and tertiary chiral amines showed that it can discriminate between these three types of amines and showed chiral discrimination for chiral secondary amines.
基于间苯二酚的深穴包合物，含有手性氨基酸的丙氨酸甲基间苯二酚酸（AMA）、丙氨酸十一烷基间苯二酚酸（AUA）和甘氨酸十一烷基间苯二酚酸（GUA），已经被合成出来。间苯二酚主体的上边缘被四个相同的取代基拉长，取代基顶端带有丙氨酸和甘氨酸基团。新型间苯二酚的结构通过核磁共振（NMR）、质谱（MS）和傅立叶变换离子回旋共振质谱中的持续离共振辐照碰撞诱导解离（SORI-CID）技术得到了阐明。这些研究表明，有八个水分子与穴包合物结合，每个丙氨酸基团结合两个水分子。推测丙氨酸取代基形成了一个风筝状的结构围绕在间苯二酚骨架周围。通过（1）H NMR 滴定研究了 AMA、AUA 和 GUA 与手性 R-和 S-甲基苄胺的结合，并与二元 L-酒石酸和单酸邻苯二甲酰丙氨酸（PA）的结合进行了比较。结果表明，这些化合物与胺类客体相互作用；然而，由于有四个羧酸基团，它们能够强烈地结合多个胺分子，而二元 L-酒石酸只能强烈地结合一个胺分子。含有一个羧酸基团的简单化合物 PA 对胺的结合较弱。AUA 与伯、仲和叔手性胺的（1）H NMR 滴定表明，它可以区分这三种类型的胺，并对手性仲胺表现出手性识别。
