$C_2$-symmetric chiral diamine ligands for enantiomeric recognition of amino acid esters and mandelic acid by proton NMR titration method

Two novel $C_2$ -symmetric chiral diamines containing $alpha$ -phenylethyl and $alpha$-(1-naphthyl)ethyl chiral subunits were prepared with quantitative yields. Enantiomeric recognition properties of these simple structured diamine ligands towards D- and L-amino acid esters and D- and L-mandelic acid were examined by the 1H NMR titration method. These ligands exhibited strong complexation (with $K_f$ up to 2481 $M^{-1}$) and good enantioselectivity (up to $K_L$ /$K_D$ = 4.08) towards the mandelic acid enantiomers. The results show that simple structured and easily accessible acyclic $C_2$-symmetrical compounds can also be used for enantiomeric recognition of racemic amino acids and mandelic acid in addition to complex molecules such as crown ethers and other cyclic molecules.

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1. Jinno, K. Ed. Chromatographic Separations Based on Molecular Recognition, VCH: Weinheim, 1996.
2. Marchi-Artzner, V.; Artzner, F.; Karthaus, O.; Shimomura, M.; Ariga, K.; Kunitake, T.; Lehn, J. M. Langmuir 1998, 14, 5164{5171.
3. Bohanon, T. M.; Caruso, P. L.; Denzinger, S.; Fink, R.; Mobius, D.; Paulus, W.; Preece, J. A.; Ringsdorf, H.; Schollmeyer, D. Langmuir 1999, 15, 174{184.
4. Pu, L. Chem. Rev. 2004, 104, 1687{1716.
5. Hembury, G. A.; Borovkov, V. V.; Inoue, Y. Chem. Rev. 2008, 108, 1{73.
6. Lehn, J. M. Supramolecular Chemistry: Concepts and Perspectives, VCH: Weinheim, 1995.
7. Chadwick, D. J.; Clie, I. A.; Sutherland, I. O. J. Chem. Soc., Perkin. Trans. 1 1984, 1707{1717.
8. Köylü, M. Z.; Aral, T.; Karakaplan, M.; Kocakaya, S. O.; Hosgoren, H. Turk. J. Chem. 2011, 35, 171{179.
9. Demirtas, H. N.; Bozkurt, S.; Durmaz, M.; Yilmaz, M.; Sirit, A. Tetrahedron 2009, 65, 3014{3018.
10. Fitzmaurice, R. J.; Kyne, G. M.; Douheret, D.; Kilburn, J. D. J. Chem. Soc., Perkin Trans. 1 2002, 6, 841{864.
11. Diederich, F. Angew. Chem., Int. Ed. Engl. 1988, 27, 362{386.
12. Aral, T.; Karakaplan, M. Tetrahedron Asymm. 2005, 16, 2119{2124.
13. Aydn, I.; Aral, T.; Karakaplan, M.; Hosgoren, H. Tetrahedron Asymm. 2009, 20, 179{183.
14. Kizirian, J. C.; Caille, J. C.; Alexakis, A. Tetrahedron Lett. 2003, 44, 8893{8895.
15. Turgut, Y.; Aral, T.; Hosgören, H. Tetrahedron Asymm. 2009, 20, 2293{2298.
16. Whitesell, J. K. Chem. Rev. 1989, 89, 1581{1590.
17. Vrettrou, M.; Gray, A. A.; Brewer, A. R. E.; Barrett, A. G. M. Tetrahedron 2007, 63, 1487{1536.
18. Voloshchuk, T.; Farina, N. S.; Wauchope, O. R.; Kiprowska, M.; Haber eld, P.; Greer, A. J. Nat. Prod. 2004, 67, 1141{1146.
19. Pospil, P. J.; Carsten, D. H.; Jacobsen, E. N. Chem. Eur. J. 1996, 2, 974{980.
20. Trost, B. M.; Bunt, R. C. J. Am. Chem. Soc. 1994, 116, 4089{4090.
21. Ohkuma, T.; Doucet, H.; Pham, T.; Mikami, K.; Korenaga, T.; Terada, M.; Noyori, R. J. Am. Chem. Soc. 1998, 120, 1086{1087.
22. Bennani, Y. L.; Hanessian, S. Chem. Rev. 1997, 97, 3161{3195.
23. Pena, C.; Gonzalez-Sabin, J.; Alfonso, I.; Rebolledo, F.; Gotor, V. Tetrahedron 2008, 64, 7709{7717.
24. Ghosh, K.; Masanta, G. Tetrahedron Lett. 2006, 47, 9233{9237.
25. Kyba, E. B.; Koga, K.; Sousa, L. R.; Siegel, M. G.; Cram, D. J. J. Am. Chem. Soc. 1973, 95, 2692-2693.
26. C olak, M.; Aral, T.; Hosgoren, H., Demirel, N. Tetrahedron Asymm. 2007, 18, 1129{1133.
27. Izatt, R. M.; Wang, T.; Hathaway, J. K.; Zhang, X. X.; Curtis, J. C.; Bradshaw, J. S.; Zhu, C. Y. J. Incl. Phenom. Mol. Recognit. Chem. 1994, 17, 157-175.
28. Yuan, Y.; Gao, G.; Jiang, Z. L.; You, J. S.; Zhou, Z. Y.; Yuan, D. Q.; Xie, R. G. Tetrahedron 2002, 58, 8993{8899.
29. Connors, K.A. Binding Constants, Wiley: New York, 1987.
30. Fielding, L. Tetrahedron 2000, 56, 6151{6170.
31. Hirose, K. J. Incl. Phenom. Macrocycl. Chem. 2001, 39, 193{209.