Tuning and enhancing enantioselective quenching of calixarene hosts by chiral guest amines.
Tuning and enhancing enantioselective quenching of calixarene hosts by chiral guest amines.
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DOI：
10.1021/ac010153k
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发表时间：
2002
影响因子：
7.4
通讯作者：
C. Lynam;K. Jennings;Kieran Nolan;Paddy Kane;M. Mckervey;D. Diamond
中科院分区：
文献类型：
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作者：
C. Lynam;K. Jennings;Kieran Nolan;Paddy Kane;M. Mckervey;D. Diamond
描述了对烯丙基杯[4]芳烃的普萘洛尔酰胺衍生物的合成，该衍生物被设计为能够根据手性胺的形状和手性来区分手性胺的分子传感器。该分子可以通过在甲醇中猝灭荧光发射来区分苯丙氨醇的对映体，而 (S)-二萘基脯氨醇杯[4]芳烃衍生物可以区分苯丙氨醇的对映体，但不能区分苯丙氨醇的对映体。可以调整萘基荧光团和手性空腔内的氢键位点之间的间隔，以识别客体胺，并在芳基和氢键位点之间具有类似的间隔。对烯丙基杯[4]芳烃普萘洛尔酰胺衍生物的金属离子络合物的形成显示出在杯[4]芳烃大环中诱导更规则和刚性的锥形构象，这显着增强了观察到的对映体辨别力。
The synthesis of a propranolol amide derivative of p-allylcalix[4]arene is described, which has been designed to behave as a molecular sensor capable of distinguishing chiral amines on the basis of their shape and chirality. This molecule can discriminate between the enantiomers of phenylalaninol through the quenching of the fluorescence emission in methanol in contrast to an (S)-dinaphthylprolinol calix[4]arene derivative, which can discriminate between the enantiomers of phenylglycinol, but not phenylalaninol. The separation between the naphthyl fluorophores and the hydrogen-bonding sites within the chiral cavity can be tuned to recognize guest amines with similar separation between aryl groups and hydrogen-bonding sites. The formation of metal ion complexes of the p-allylcalix[4]arene propranolol amide derivative is shown to induce a more regular and rigid cone conformation in the calix[4]arene macrocycle, which generates a significant enhancement in the observed enantiomeric discrimination.