α-氨氧基酸诱导的手性N-O转角的合成与表征

Synthesis and characterization of chiral N-O turns induced by alpha-aminoxy acids.

作者信息

Yang D, Li B, Ng F F, Yan Y L, Qu J, Wu Y D

机构信息

Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong.

出版信息

J Org Chem. 2001 Nov 2;66(22):7303-12. doi: 10.1021/jo010376a.

DOI:10.1021/jo010376a

PMID:11681942

Abstract

Chiral alpha-aminoxy acids of various side chains were synthesized with high optical purity starting from chiral alpha-amino acids. The conformations of diamides 13a-e, 15, and 16 were probed by using NMR, FT-IR, and CD spectroscopic methods as well as X-ray crystallography. The right-handed turns with eight-membered-ring intramolecular hydrogen bonds between adjacent residues (called the N-O turns) were found to be preferred for D-aminoxy acid residues, and they were independent of the side chains. The rigid chiral N-O turns should have great potential in molecular design.

摘要

以手性α-氨基酸为起始原料，合成了具有不同侧链的手性α-氨氧基酸，其光学纯度较高。通过核磁共振（NMR）、傅里叶变换红外光谱（FT-IR）、圆二色光谱（CD）以及X射线晶体学等方法对二酰胺13a - e、15和16的构象进行了探究。发现对于D-氨氧基酸残基而言，相邻残基之间形成八元环分子内氢键的右手螺旋（称为N-O螺旋）是较为有利的构象，且它们与侧链无关。这种刚性的手性N-O螺旋在分子设计中应具有巨大的潜力。