Differentiation of enantiomeric anions by NMR spectroscopy with chiral bisurea receptors

被引:20
作者
Ito, Suguru [1 ]
Okuno, Manami [1 ]
Asami, Masatoshi [1 ]
机构
[1] Yokohama Natl Univ, Grad Sch Engn, Dept Adv Mat Chem, Hodogaya Ku, 79-5 Tokiwadai, Yokohama, Kanagawa 2408501, Japan
关键词
SOLVATING AGENTS; ENANTIOSELECTIVE ADDITION; UREA DERIVATIVES; CARBOXYLIC-ACIDS; AMINO-ACIDS; RECOGNITION; DISCRIMINATION; BINDING; ENANTIODISCRIMINATION; BIS(THIOUREA);
D O I
10.1039/c7ob02318a
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Chiral anionic species are ubiquitous and play important roles in biological systems. Despite the recent advancements in synthetic anion receptors bearing urea functionalities, urea-based chiral solvating agents (CSAs) that can separate the NMR signals of racemic anions remain limited. Herein, three dibenzofuran-based C-2-symmetric chiral bisureas were synthesized from the reaction of (R,R)-4,6-bis(1-aminopropyl) dibenzo[b, d] furan with phenyl isocyanate, phenyl thioisocyanate, or tosyl isocyanate. The chiral anion recognition properties of these bisureas were examined by H-1 NMR spectroscopy using DL-tetra-butylammonium mandelate (TBAM) as a model substrate. A clear baseline separation of the enantiomeric signals of the benzylic proton of TBAM was achieved upon mixing with 0.5 equivalents of bis(phenylurea). In contrast to previous urea-based chiral anion receptors that differentiate the enantiomers of chiral anions by forming 1 : 1 host-guest complexes, a high chiral recognition ability of chiral bis(phenylurea) was achieved owing to the generation of an equilibrium between free guests, 1 : 1 host-guest complexes, and 1 : 2 host-guest complexes. Chiral bis(phenylurea) was also successfully employed in the separation of the enantiomeric H-1 NMR signals of various racemic anions.
引用
收藏
页码:213 / 222
页数:10
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