Chirality Conversion of Dipeptides in the Schiff Bases of Binol Aldehydes with Multiple Hydrogen Bond Donors

Bulletin of the Korean chemical society

Hyunjung Park¹  Kwan Mook Kim¹  Jooyeon Hong¹  Sihyun Ham¹  Raju Nandhakumar¹ 

关键词: Deracemization;    Schiff base;    Dipeptide;    Stereoselective recognition;    DFT calculation;   

DOI  :  

学科分类：化学（综合）

来源: Korean Chemical Society

【 摘 要 】

Novel binol aldehydes derivatized at 2` hydroxy position with both uryl and acetamide groups (2), and diuryl groups (3) have been synthesized. Both were designed for streospecific binding and chirality conversion of general dipeptides with support of multiple hydrogen bonding donor sites in the receptors. The receptors, 2 and 3, converted the chirality of N-terminal amino acids of peptides such as Ala-Gly, Met-Gly, Leu-Gly and His-Gly with stereoselectivity on D-form over L-form. The stereoselectivity ratios were in the range of 5-11, somewhat higher than those of the binol receptor with mono uryl group (1). The DFT calculation at the B3LYP/6-31G*//MPWB1K/6-31G* level revealed that 3-D-Ala-Gly was 2.2 kcal/mol more stable than 3-L-Ala-Gly. The considerable steric hindrance between the methyl group of the alanine and the imine CH moiety of the receptor seems to be the main contributing factor for the thermodynamic preference.

【 授权许可】

Unknown