Macroscopic expression of the chirality of amino alcohols by a double amplification mechanism in liquid crystalline media

Journal of the American Chemical Society

Volumn 127, Issue 39, 2005, Pages 13480-13481

  Eelkema, Rienk ^a   Feringa, Ben L ^a  

^a UNIVERSITY OF GRONINGEN   (Netherlands)

Author keywords

[No Author keywords available]

Indexed keywords

AMINOALCOHOL;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL INTERACTION; CHEMICAL STRUCTURE; CHIRALITY; CIRCULAR DICHROISM; COMPLEX FORMATION; CONCENTRATION RESPONSE; CONFORMATIONAL TRANSITION; COVALENT BOND; DIASTEREOISOMER; ENANTIOMER; HYDROGEN BOND; LIQUID CRYSTAL; MEASUREMENT; PARAMETER; STEREOCHEMISTRY; STOICHIOMETRY; STRUCTURE ANALYSIS; SUPRAMOLECULAR CHEMISTRY; TECHNIQUE;

EID: 25844461768     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja054352n     Document Type: Article

References (29)

1. (a) Feringa, B. L.; van Delden, R. A. Angew. Chem., Int. Ed. 1999, 38, 3418-3438.
2. (b) Cintas, P. Angew. Chem., Int. Ed. 2002, 41, 1139-1145.
3. Yashima, E.; Maeda, K.; Nishimura, T. Chem.-Eur. J. 2004, 10, 42-51.
4. (a) Bertocchi, G.; Gottarelli, G.; Prati, R. Talanta 1984, 31, 138-140.
5. (b) Gottarelli, G.; Samori, B.; Fuganti, C.; Grasselli, P. J. Am. Chem. Soc. 1981, 103, 471-472.
6. Soai, K.; Sato, I.; Shibata, T. Chem. Rec. 2001, 1, 321-332.
7. (a) Hirschberg, J. H. K. K.; Brunsveld, L.; Ramzi, A.; Vekemans, J. A. J. M.; Sijbesma, R. P.; Meijer, E. W. Nature 2000, 407, 167-170.
8. (b) Prins, L. J.; Timmerman, P.; Reinhoudt, D. N. J. Am. Chem. Soc. 2001, 123, 10153-10163.
9. (c) De Jong, J. J. D.; Lucas, L. N.; Kellogg, R. M.; van Esch, J. H.; Feringa, B. L. Science 2004, 304, 278-281.
10. Green, M. M.; Park, J.-W.; Sato, T.; Teramoto, A.; Lifson, S.; Selinger, R. L. B.; Selinger, J. V. Angew. Chem., Int. Ed. 1999, 38, 3138-3154.
11. Huck, N. P. M.; Jager, W. F.; de Lange, B.; Feringa, B. L. Science 1996, 273, 1686-1688.
12. (a) Coles, H. In Handbook of Liquid Crystals, Vol. 2A: Low Molecular Weight Liquid Crystals I; Demus, D., Goodby, J., Gray, G. W., Spiess, H.-W., Vill V., Eds.; Wiley-VCH: Weinheim, 1998; pp 336-337.
13. (b) Allenmark, S. Chirality 2003, 15, 409-422.
14. (c) Yoshida, J.; Sato, H.; Yamagishi, A.; Hoshino, N. J. Am. Chem. Soc. 2005, 127, 8453-8456.
15. The pitch is generally determined by the Grandjean-Cano technique, a method which requires an aligned LC sample to be placed between a plane-convex lens and a flat surface. The pitch can then be obtained from the distances between the distinct lines seen through a polarizing microscope. See: Heppke, G.; Oestreicher, F. Mol. Cryst. Liq. Cryst. 1977, 41, 245-249.
16. Superchi, S.; Donnoli, M. I.; Proni, G.; Spada, G. P.; Rosini, C. J. Org. Chem. 1999, 64, 4762-4767 and references therein.
17. van Delden, R. A.; Feringa, B. L. Angew. Chem., Int. Ed. 2001, 40, 3198-3200.
18. Reetz, M. T. Angew. Chem., Int. Ed. 2002, 41, 1335-1338.
19. (a) Pu, L. Chem. Rev. 2004, 104, 1687-1716.
20. (b) Wojciechowski, G.; Rozwadowski, Z.; Dziembowska, T.; Brzezinski, B. J. Mol. Struct. 2001, 559, 379-389 and references therein.
21. Holzwarth, R.; Bartsch, R.; Cherkaoui, Z.; Solladié, G. Chem.-Eur. J. 2004, 10, 3931-3935 and references therein.
22. See Supporting Information for details.
23. Yamaguchi, T.; Inagawa, T.; Nakazumi, H.; Irie, S.; Irie, M. J. Mater. Chem. 2001, 11, 2453-2458.
24. At higher amino alcohol to biphenol ratios, partial phase separation was observed. At lower ratios, highly disturbed phases were obtained, of which the pitch was found to be impossible to measure, although wormlike textures were still observed, indicating a cholesteric phase.
25. Interestingly, using this new principle it is also possible to amplify the chirality of a molecule with a measurable helical twisting power. 1-N,N-dimethylphenylalaninol in E7 has a pitch of 11 μm, whereas the uncomplexed amino alcohol, at the same concentration, gives rise to a pitch of 28 μm.
26. The presence of an arene moiety in the amino alcohol appears to be essential, as complexes of aliphatic amino alcohols valinol and t-leucinol in E7 had pitches that were too large to measure; IR studies did not indicate participation of nitrile groups (as present in E7).
27. While this work was in progress, a paper describing the diastereoselective binding of chiral amines to biphenols appeared: Takagi, H.; Mizutani, T.; Horiguchi, T.; Kitagawa, S.; Ogoshi, H. Org. Biomol. Chem. 2005, 3, 2091-2094.
28. The wavelength of reflection, when perpendicular to the surface, is equal to the refractive index of the material times the pitch.
29. Eelkema, R.; van Delden, R. A.; Feringa, B. L. Angew. Chem., Int. Ed. 2004, 43, 5013-5016 and references therein.