大环手性磷酰胺对氨基酸衍生物的分子识别研究

以(S)-α-甲基苯乙胺和天然氨基酸(L-丙氨酸、L-苯甘氨酸及L-苯丙氨酸)为手性源,以2,5-二(邻羟基苯基)-1,3,4- 二唑和2,4-二(邻羟基苯基)-1,3,5- 二唑为刚性单元,合成了一系列具有光学活性的新型含 二唑磷酰胺和磷酯手性大环化合物.用NMR,IR和FABMS方法研究了所合成的手性大环对氨基酸甲酯盐酸盐和二肽的分子间相互作用和分子识别.结果表明,这些主体对D-或L-氨基酸甲酯盐酸盐和二肽具有选择性的结合作用.

Studies on Molecular Recognition of Amino Acid Derivatives by Macrocyclic Chiral Phosphoramidates

In this paper, a series of new chiral macrocyclic phosphoramidates containing 2,5-diaryl- 1,3,4-oxadizole and (S)-methylbenzylamine and L-amino acid methyl ester units were synthesized and the structures were determined by 1H NMR, MS, IR spectra and elemental analyses. FABMS, NMR and IR techniques were used to study the molecular recognition phenomena. The phosphoramidate molecules can form hydrogen bond or aromatic π-π interaction with D-phenylglycine, L-phenylglycine or L-phenylalanine methyl ester hydrochloride and dipeptide according to the appearance of 1+1 host guest molecular peak in FABMS spectra, NMR chemical shift and coupling constant changes. The chiral molecular recognition ability of chiral macrocyclic phosphoramidate for D-phenylglycine methyl ester hydrochloride is stronger than L-phenylglycine methyl ester hydrochloride. The side chain also affect the recognition ability, smaller substituent is better than larger substituent for the recongnition. As for the guest molecules, the {D-phenylglycine} and L-phenylglycine methyl ester hydrochloride are better than D- or L-phenylalanine methyl ester hydrochloride for the recongnition, no inclusion for the D- or L-alanine and L-histine methyl ester hydrochloride.