Relationship between chirality content and stereoinduction: Identification of a chiraphore [18]

Journal of the American Chemical Society

Volumn 121, Issue 40, 1999, Pages 9481-9482

  Gao, Daquan ^a   Schefzick, Sabine ^a   Lipkowitz, Kenny B ^a  

^a INDIANA UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; CATALYST; CHEMICAL STRUCTURE; CHEMOMETRIC ANALYSIS; CHIRALITY; ENANTIOMER; LETTER; STEREOCHEMISTRY; STEREOISOMERISM;

EID: 0033552268     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja991391o     Document Type: Letter

References (11)

1. New Developments in Molecular Chirality; Mezey, P. G., Ed.; Kluwer: Dordrecht, 1991; chapters therein.
2. For additional review articles, see: (a) Buda, A. B.; Auf der Heyde, T.; Mislow, K. Angew. Chem., Int. Ed. Engl. 1992, 31, 989. (b) Gilat, G. In Concepts in Chemistry: A Contemporary Challenge; Rouvray, D. H., Ed., Research Studies Press: Taunton, 1996, Chapter 10, pp 325-354. (c) Avnir, D.; Katzenelson, O.; Keinan, S.; Pinsky, M.; Pinto, Y.; Salomon, Y.; Zabrodsky Hel-Or, H. ibid; Chapter 10, pp 283-324.
3. For additional review articles, see: (a) Buda, A. B.; Auf der Heyde, T.; Mislow, K. Angew. Chem., Int. Ed. Engl. 1992, 31, 989. (b) Gilat, G. In Concepts in Chemistry: A Contemporary Challenge; Rouvray, D. H., Ed., Research Studies Press: Taunton, 1996, Chapter 10, pp 325-354. (c) Avnir, D.; Katzenelson, O.; Keinan, S.; Pinsky, M.; Pinto, Y.; Salomon, Y.; Zabrodsky Hel-Or, H. ibid; Chapter 10, pp 283-324.
4. For additional review articles, see: (a) Buda, A. B.; Auf der Heyde, T.; Mislow, K. Angew. Chem., Int. Ed. Engl. 1992, 31, 989. (b) Gilat, G. In Concepts in Chemistry: A Contemporary Challenge; Rouvray, D. H., Ed., Research Studies Press: Taunton, 1996, Chapter 10, pp 325-354. (c) Avnir, D.; Katzenelson, O.; Keinan, S.; Pinsky, M.; Pinto, Y.; Salomon, Y.; Zabrodsky Hel-Or, H. ibid; Chapter 10, pp 283-324.
5. Osipov, M. A.; Pickup, B. T.; Dunmur, D. A. Mol. Phys. 1995, 84, 1193.
6. Grant, J. A.; Gallardo, M. A.; Pickup, B. T. J. Comput. Chem. 1996, 17, 1653.
7. Zabrodsky, H.; Avnir, D. J. Am. Chem. Soc. 1995, 117(1), 462.
8. The ability of the CCM approach to quantify structure - activity correlations in bioreceptors has been published: Keinan, S.; Avnir, D. J. Am. Chem. Soc. 1998, 120(24), 6152.
9. Harada, T.; Takeuchi, M.; Hatsuda, M.; Ueda, H.; Oku, A. Tetrahedron: Asymmetry 1996, 2479.
10. Conformational searches of the pendant groups in compounds 2-3 were carried oui with the grid-based method of Spartan version 4.1, Wavefunction Inc., 18401 Von Karman, Suite 370, Irvine, CA 92715. The same metal and semiempirical Hamiltonian used in ref 7 was implemented by us. The lowest energy conformer for all systems evaluated was used Io determine the bi-aryl twist angle and also for the CCM calculations.
11. A reviewer remains skeptical that the chirality metrics offer any advantages over the dihedral angle. In addition to providing a quantitative measure of chirality (something a dihedral angle does not provide) we point out that due to the warping of the aryl rings the value of the dihedral angle will change, depending upon which atoms are used to define that internal coordinate (in compound 2a, for instance, the value is 56.5° when the four contiguous atoms are those proximal to the hydroxyls, while it is 54.5° when the four distal atoms are used instead; in another system we have been studying the differences are as large as 6°).