Novel chiral hexaazamacrocycles for the enantiodiscrimination of carboxylic acids

作者：Gospodarowicz Krzysztof; Holynska Malgorzata; Paluch Marta; Lisowski Jerzy^*

来源：Tetrahedron, 2012, 68(48): 9930-9935.

DOI：10.1016/j.tet.2012.09.093

• Macrocycles
• Chiral recognition
• Carboxylic acids
• Amines
• Solvating agents

New enantiopure amines (R,R)-1 and (S,S)-1 were obtained from (R)- or (S)-2,2%26apos;-diamino-1,1%26apos;-binaphthyl and 2,6-diformylpyridine in a synthesis templated by lead(II) or lanthanide(III) ions, reduction with NaBH4 and subsequent demetallation. Similarly new amines (R,R,R,R)-2 and (S,S,S,S)-2 were obtained from (1R, 2R)- or (1S, 2S)-1,2-diphenylethylenediamine. The X-ray crystal structure of the Pb(II) complex with macrocyclic Schiff base precursor of (R,R)-1 indicates helical twisted conformation of this macrocycle, while the ROESY spectrum of R,R-1 suggests less twisted conformation. (R,R)-1 and (R,R,R,R)-2 were tested as chiral shift reagents (chiral solvating agents) for various alpha-substituted carboxylic acids, including non steroidal anti-inflammatory drugs. Enantiodiscrimination of carboxylate H-1 NMR signals was observed with Delta Delta delta values up to 0.1 ppm.

• 出版日期2012-12-2