Chemistry of unique chiral olefins. 2. Unexpected thermal racemization of cis-1,1',2,2',3,3',4,4'-octahydro-4,4'biphenanthrylidene

Journal of the American Chemical Society

Volumn 119, Issue 31, 1997, Pages 7249-7255

  Harada, Nobuyuki ^a,b   Saito, Akira ^a   Koumura, Nagatoshi ^a   Roe, D Christopher ^b   Jager, Wolter F ^c   Zijlstra, Robert W J ^c   De Lange, Ben ^c   Feringa, Ben L ^c  

^a TOHOKU UNIVERSITY   (Japan)

^b DUPONT COMPANY   (United States)

^c UNIVERSITY OF GRONINGEN   (Netherlands)

Author keywords

[No Author keywords available]

Indexed keywords

PHENANTHRENE DERIVATIVE;

ARTICLE; CIRCULAR DICHROISM; DRUG STABILITY; DRUG STRUCTURE; ENTHALPY; ENTROPY; ISOMERISM; NUCLEAR OVERHAUSER EFFECT; OPTICAL ROTATION; REACTION ANALYSIS; STEREOCHEMISTRY; TEMPERATURE; X RAY CRYSTALLOGRAPHY;

EID: 0030742710     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja970668m     Document Type: Article

References (18)

1. See papers of this series: (a) (part 1), Harada, N.; Saito, A.; Koumura, N.; Uda, H.; de Lange, B.; Jager, W. F.; Wynberg, H.; Feringa, B. L. J. Am. Chem. Soc. 1997, 119, 7241. (b) (part 3), Harada, N.; Koumura, N.; Feringa, B. L. J. Am. Chem. Soc. 1997, 119, 7256.
2. See papers of this series: (a) (part 1), Harada, N.; Saito, A.; Koumura, N.; Uda, H.; de Lange, B.; Jager, W. F.; Wynberg, H.; Feringa, B. L. J. Am. Chem. Soc. 1997, 119, 7241. (b) (part 3), Harada, N.; Koumura, N.; Feringa, B. L. J. Am. Chem. Soc. 1997, 119, 7256.
3. See: Feringa, B.; Wynberg, H. J. Am. Chem. Soc. 1977, 99, 602.
4. See also other chiral olefins: Feringa, B. L.; Jager, W. F.; de Lange, B.; Meijer, E. W. J. Am. Chem. Soc. 1991, 113, 5468. Jager, W. F.; de Jong, J. C.; de Lange, B.; Huck, N. P. M.; Meetsma, A.; Feringa, B. L. Angew. Chem., Int. Ed. Engl. 1995, 34, 348 and references cited therein.
5. See also other chiral olefins: Feringa, B. L.; Jager, W. F.; de Lange, B.; Meijer, E. W. J. Am. Chem. Soc. 1991, 113, 5468. Jager, W. F.; de Jong, J. C.; de Lange, B.; Huck, N. P. M.; Meetsma, A.; Feringa, B. L. Angew. Chem., Int. Ed. Engl. 1995, 34, 348 and references cited therein.
6. See also: Huck, N. P. M.; Jager, W. F.; de Lange, B.; Feringa, B. L. Science 1996, 273, 1686. Feringa, B. L.; Huck, N. P. M.; van Doren, H. A. J. Am. Chem. Soc. 1995, 117, 9929 and references cited therein.
7. See also: Huck, N. P. M.; Jager, W. F.; de Lange, B.; Feringa, B. L. Science 1996, 273, 1686. Feringa, B. L.; Huck, N. P. M.; van Doren, H. A. J. Am. Chem. Soc. 1995, 117, 9929 and references cited therein.
8. For a review about (hetero)helicenes, see: (a) Prinsen, W. J. C.; Laarhoven, W. H. In Topics in Current Chemistry 125; Vögtle, F., Weber, E., Eds.; Springer-Verlag: Berlin, Heidelberg, 1984. (b) Martin, R. H. Angew. Chem. 1974, 86, 727. Martin, R. H. Angew. Chem., Int. Ed. Engl. 1974, 13, 649. (c) Wynberg, H. Acc. Chem. Res. 1971, 4, 65.
9. For a review about (hetero)helicenes, see: (a) Prinsen, W. J. C.; Laarhoven, W. H. In Topics in Current Chemistry 125; Vögtle, F., Weber, E., Eds.; Springer-Verlag: Berlin, Heidelberg, 1984. (b) Martin, R. H. Angew. Chem. 1974, 86, 727. Martin, R. H. Angew. Chem., Int. Ed. Engl. 1974, 13, 649. (c) Wynberg, H. Acc. Chem. Res. 1971, 4, 65.
10. For a review about (hetero)helicenes, see: (a) Prinsen, W. J. C.; Laarhoven, W. H. In Topics in Current Chemistry 125; Vögtle, F., Weber, E., Eds.; Springer-Verlag: Berlin, Heidelberg, 1984. (b) Martin, R. H. Angew. Chem. 1974, 86, 727. Martin, R. H. Angew. Chem., Int. Ed. Engl. 1974, 13, 649. (c) Wynberg, H. Acc. Chem. Res. 1971, 4, 65.
11. For a review about (hetero)helicenes, see: (a) Prinsen, W. J. C.; Laarhoven, W. H. In Topics in Current Chemistry 125; Vögtle, F., Weber, E., Eds.; Springer-Verlag: Berlin, Heidelberg, 1984. (b) Martin, R. H. Angew. Chem. 1974, 86, 727. Martin, R. H. Angew. Chem., Int. Ed. Engl. 1974, 13, 649. (c) Wynberg, H. Acc. Chem. Res. 1971, 4, 65.
12. For a review about (hetero)helicenes, see: (a) Prinsen, W. J. C.; Laarhoven, W. H. In Topics in Current Chemistry 125; Vögtle, F., Weber, E., Eds.; Springer-Verlag: Berlin, Heidelberg, 1984. (b) Martin, R. H. Angew. Chem. 1974, 86, 727. Martin, R. H. Angew. Chem., Int. Ed. Engl. 1974, 13, 649. (c) Wynberg, H. Acc. Chem. Res. 1971, 4, 65.
13. Passerini, R.; Ross, I. G. J. Sci. Instr. 1953, 30, 274.
14. Schuddeboom, W.; Jonker, S. A.; Warman, J. M.; de Haas, M. P.; Vermeulen, M. J. W.; Jager, W. F.; de Lange, B.; Feringa, B. L.; Fessenden, R. W. J. Am. Chem. Soc. 1993, 115, 3286.
15. For the racemization of first-order reaction, the decrease of enantiomeric excess is formulated as -d([5] - [R])/dt = k′([S] - [R]) where [S] and [R] are the concentration of enantiomers S and R, respectively, and k′ is the apparent rate constant of racemization obtained from CD or NMR data. The equation is expressed as -d[S]/dt + d[R]/dt = k′([S] - [R]). On the other hand, the increase of S enantiomer in an enamiomeric interconversion system is formulated as d[S]/dt = -k[S] + k[R] where k is the actual rate constant of enantiomeric isomenzation Similarly, d[R]/dt = k[S] - k[R]. Subtraction of d[S]/dt = -k[S] + k[R] from d[R]/dt = k[S] - k[R] gives -d[S]/dt + d[R]/dt = 2k[S] - [R]). From this equation and -d[S]/ dt + d[R]/dt = k′([S] - [R]), k = k′/2. Namely, the rate constant of enantiomeric interconversion is half of the rate constant of racemization.
16. Sandstrom, J. Dynamic NMR Spectroscopy; Academic Press: London and New York, 1982.
17. Chenard, B. L.; Dixon, D. A.; Harlow, R. L.; Roe, C. D.; Fukunaga, T. J. Org. Chem. 1987, 52, 2411.
18. Forsen, S.; Hoffman, R. A. J. Chem. Phys. 1963, 39, 2892.