Axial Chirality in 1,4-Disubstituted (ZZ)-1,3-Dienes. Surprisingly Low Energies of Activation for the Enantiomerization in Synthetically Useful Fluxional Molecules

Journal of the American Chemical Society

Volumn 125, Issue 50, 2003, Pages 15402-15410

  Warren, Sandra ^a   Chow, Albert ^a   Fraenkel, Gideon ^a   Rajanbabu, T V ^a  

^a OHIO STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

LINE SHAPE ANALYSIS;

CHEMICAL BONDS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; ORGANOMETALLICS; THERMAL EFFECTS;

POLYSILICON;

ALKADIENE; LEAD; PHOSPHINE DERIVATIVE; SILICON; TIN; TIN DERIVATIVE; TRISPENTAFLUOROPHENYLPHOSPHINE; UNCLASSIFIED DRUG;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CHEMICAL BOND; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; CHIRALITY; ENANTIOMER; GEOMETRY; LOW TEMPERATURE PROCEDURES; PROTON NUCLEAR MAGNETIC RESONANCE; SYNTHESIS;

EID: 0346850025     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja035136m     Document Type: Article

References (35)

1. For two recent reviews, see: (a) Lloyd-Williams, P.; Giralt, E. Chem. Soc. Rev. 2001, 30, 145.
2. (b) Bringmann, G.; Breuning, M.; Tasler, S. Synthesis 1999, 525.
3. Ojima, I., Ed. Catalytic Asymetric Synthesis, 2nd ed.; Wiley-VCH: New York, 2000.
4. (b) Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Comprehensive Asymmetric Catalysis; Springer-Verlag: Berlin, 1999.
5. (a) Eliel, E. L.; Wilen, S. H. Stereochemistry, of Organic Compounds: Wiley: New York, 1994. pp 1142-1166.
6. For recent examples see, (b) Kitagawa, O.; Izawa, H.; Sato, K.; Dobashi, A.; Taguchi, T. J. Org. Chem. 1998, 63, 2634.
7. (c) Clyden, J. Synlett 1998, 810.
8. (d) Curran, D. P.; Hale, G. R.; Geib, S. J.; Balog, A.; Cass, Q. B.; Degani, A. L. G.; Hermandes, M. Z.; Freitas, L. C. G. Tetrahedron: Asymmetry 1997, 8, 3955.
9. (e) Godfrey, C. R. A.; Simpkins, N. S.; Walker, M. D. Synlett. 2000, 388.
10. (f) Rios, R.; Jimeno, C.; Carroll, P. J.; Walsh, P. J. J. Am. Chem. Soc. 2002, 124, 10 272.
11. Boer, F. P.; Doorakian, G. A.; Freedman, H. H.; McKinley, S. V. J. Am. Chem. Soc. 1970, 92, 1225. For a preliminary report, see, Boer, F. P.; Flynn, J. J.; Freedman, H. H.; McKinley, S. V.; Sandel, V. R. J. Am. Chem. Soc. 1967, 89, 5068.
12. Boer, F. P.; Doorakian, G. A.; Freedman, H. H.; McKinley, S. V. J. Am. Chem. Soc. 1970, 92, 1225. For a preliminary report, see, Boer, F. P.; Flynn, J. J.; Freedman, H. H.; McKinley, S. V.; Sandel, V. R. J. Am. Chem. Soc. 1967, 89, 5068.
13. Köbrich, G.; Mannschreck, A.; Misra, R. A.; Rissmann, G.; Rösner, M.; Zündorf, W. Chem. Ber. 1972, 105, 3794. See also, Köbrich, G.; Kolb, B.; Mannschreck, A.; Misra, R. A. Chem. Ber. 1973, 106, 1601.; Mannschreck, A.; Jonas, V.; Bödecker, H.-O.; Elbe, H.-L.; Köbrich, G. Tetrahedron Lett. 1974, 2153.; For another example, see. Bomse, D. S.; Morton, T. H. Tetrahedron Lett. 1974, 3491.
14. Köbrich, G.; Mannschreck, A.; Misra, R. A.; Rissmann, G.; Rösner, M.; Zündorf, W. Chem. Ber. 1972, 105, 3794. See also, Köbrich, G.; Kolb, B.; Mannschreck, A.; Misra, R. A. Chem. Ber. 1973, 106, 1601.; Mannschreck, A.; Jonas, V.; Bödecker, H.-O.; Elbe, H.-L.; Köbrich, G. Tetrahedron Lett. 1974, 2153.; For another example, see. Bomse, D. S.; Morton, T. H. Tetrahedron Lett. 1974, 3491.
15. Köbrich, G.; Mannschreck, A.; Misra, R. A.; Rissmann, G.; Rösner, M.; Zündorf, W. Chem. Ber. 1972, 105, 3794. See also, Köbrich, G.; Kolb, B.; Mannschreck, A.; Misra, R. A. Chem. Ber. 1973, 106, 1601.; Mannschreck, A.; Jonas, V.; Bödecker, H.-O.; Elbe, H.-L.; Köbrich, G. Tetrahedron Lett. 1974, 2153.; For another example, see. Bomse, D. S.; Morton, T. H. Tetrahedron Lett. 1974, 3491.
16. Köbrich, G.; Mannschreck, A.; Misra, R. A.; Rissmann, G.; Rösner, M.; Zündorf, W. Chem. Ber. 1972, 105, 3794. See also, Köbrich, G.; Kolb, B.; Mannschreck, A.; Misra, R. A. Chem. Ber. 1973, 106, 1601.; Mannschreck, A.; Jonas, V.; Bödecker, H.-O.; Elbe, H.-L.; Köbrich, G. Tetrahedron Lett. 1974, 2153.; For another example, see. Bomse, D. S.; Morton, T. H. Tetrahedron Lett. 1974, 3491.
17. Rösner, M.; Köbrich, G. Angew. Chem. Int. Ed. Engl. 1974, 13, 741.
18. Pasto, D. J.; Borchardt, J. K. J. Am. Chem. Soc. 1974, 96, 6220.
19. Jelinski, L. W.; Kiefer, E. F. J. Am. Chem. Soc. 1976, 98, 281.
20. Pasto, D. J.; Scheidt, W. R. J. Org. Chem. 1975, 40, 1444.
21. Gréau, S.; Radetich, B.; RajanBabu, T. V. J. Am. Chem. Soc. 2000, 122, 8579.
22. (a) See the Supporting Information for details and spectra.
23. (b) Graphical representations of the temperature dependence of chemical shifts of the relevant protons are included in the Supporting Information.
24. Kaplan, J. I.; Fraenkel, G. NMR of Chemically Exchanging Systems; Academic Press: New York, 1980.
25. The effective sizes of groups are different whether they are in a cis-1,3-synaxial relationship as in 1,3-cyclohexanes or in the 2,2-positions of a 1,1′-binaphthyl system. In the latter case, the groups are pointed at each other and the interactions increase as the van der Waals radii or the bond lengths increase. See Eliel, E. L.; Wilen, S. H.; Mander, L. N. Stereochemistry, of Organic Compounds, Wiley: New York, 1994; p. 1144.
26. Jelinski, L. W.; Kiefer, E. F. J. Am. Chem. Soc. 1976, 98, 282.
27. (a) Mislow, K. Acc. Chem. Res. 1976, 9, 26
28. (b) Gust, D.; Mislow, K. J. Am. Chem. Soc. 1973, 95, 1535.
29. (c) Finocchiaro, P.; Gust, D.; Mislow, K. J. Am. Chem. Soc. 1973, 95, 7029.
30. (d) Hummel, J. P.; Gust, D.; Mislow, K. J. Am. Chem. Soc. 1974, 96, 3679.
31. (e) Blount, J. B.; Finocchiaro, P.; Gust, D.; Mislow, K. J. Am. Chem. Soc. 1973, 95, 7019.
32. An intriguing mechanistic possibility for the helix inversion involves a series of conrotatory electrocyclic ring closures and openings as shown below. However, this remains highly speculative since we have not seen any evidence of the cyclobutene or of the (EE)-diene in any of the spectroscopic or chemical experiments. (diagram presented)
33. Saunders: M.; Yamada, F. J. Am. Chem. Soc. 1963, 85, 1882.
34. Van Geet, A. L. Anal. Chem. 1970, 42, 679.
35. Chenard, B. L.; Laganis, E. D.; Davidson, F.; RajanBabu, T. V. J. Org. Chem. 1985, 50, 3666.