Stereocontrolled synthesis of angularly substituted 1-azabicyclic rings by cationic 2-aza-cope rearrangements

Organic Letters

Volumn 7, Issue 5, 2005, Pages 913-916

  Aron, Zachary D ^a   Overman, Larry E ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATION; HETEROCYCLIC COMPOUND;

ARTICLE; CHEMICAL STRUCTURE; NUCLEAR OVERHAUSER EFFECT; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STEREOCHEMISTRY; STRUCTURE ANALYSIS; SUBSTITUTION REACTION; SYNTHESIS;

AZA COMPOUNDS; BICYCLO COMPOUNDS, HETEROCYCLIC; CATALYSIS; COMBINATORIAL CHEMISTRY TECHNIQUES; INDICATORS AND REAGENTS; MOLECULAR STRUCTURE; STEREOISOMERISM;

EID: 15044342205     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol047330z     Document Type: Article

References (31)

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12. For brief reviews, see: (c) Overman, L. E. Acc. Chem. Res. 1992, 25, 352-359. (d) Overman, L. E. Aldrichem, Acta 1995, 28, 107-120. (e) Royer, J.; Bonin, M.; Micouin, L. Chem. Rev. 2004, 104, 2311-2352.
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14. For representative examples, see: (a) Rischke, H.; Wilcock, J.; Winterfeldt, E. Chem. Ber. 1973, 106, 3106-3118. (b) Mooiweer, H. H.; Hiemstra, H.; Speckamp, W. N. Tetrahedron 1991, 47, 3451-3462. (c) Gelas-Mailhe, Y.; Gramain, J. C.; Louvet, A.; Remuson, R. Tetrahedron Lett. 1992, 33, 73-76. (d) ref 4b.
15. For representative examples, see: (a) Rischke, H.; Wilcock, J.; Winterfeldt, E. Chem. Ber. 1973, 106, 3106-3118. (b) Mooiweer, H. H.; Hiemstra, H.; Speckamp, W. N. Tetrahedron 1991, 47, 3451-3462. (c) Gelas-Mailhe, Y.; Gramain, J. C.; Louvet, A.; Remuson, R. Tetrahedron Lett. 1992, 33, 73-76. (d) ref 4b.
16. For representative examples, see: (a) Rischke, H.; Wilcock, J.; Winterfeldt, E. Chem. Ber. 1973, 106, 3106-3118. (b) Mooiweer, H. H.; Hiemstra, H.; Speckamp, W. N. Tetrahedron 1991, 47, 3451-3462. (c) Gelas-Mailhe, Y.; Gramain, J. C.; Louvet, A.; Remuson, R. Tetrahedron Lett. 1992, 33, 73-76. (d) ref 4b.
17. For representative examples, see: (a) Overman, L. E.; Yokomatsu, T. J. Org. Chem. 1980, 45, 5229-5230. (b) Castelhano, A. L.; Krantz, A. J. Am. Chem. Soc. 1984, 106, 1877-1879. (c) Hart, D. J.; Yang, T.-K. J. Org. Chem. 1985, 50, 235-242. (d) Agami, C.; Couty, F.; Poursoulis, M. Synlett 1992, 847-848. (e) Bennett, D. J.; Hamilton, N. M. Tetrahedron Lett. 2000, 41, 7961-7964. (f) ref 4b.
18. For representative examples, see: (a) Overman, L. E.; Yokomatsu, T. J. Org. Chem. 1980, 45, 5229-5230. (b) Castelhano, A. L.; Krantz, A. J. Am. Chem. Soc. 1984, 106, 1877-1879. (c) Hart, D. J.; Yang, T.-K. J. Org. Chem. 1985, 50, 235-242. (d) Agami, C.; Couty, F.; Poursoulis, M. Synlett 1992, 847-848. (e) Bennett, D. J.; Hamilton, N. M. Tetrahedron Lett. 2000, 41, 7961-7964. (f) ref 4b.
19. For representative examples, see: (a) Overman, L. E.; Yokomatsu, T. J. Org. Chem. 1980, 45, 5229-5230. (b) Castelhano, A. L.; Krantz, A. J. Am. Chem. Soc. 1984, 106, 1877-1879. (c) Hart, D. J.; Yang, T.-K. J. Org. Chem. 1985, 50, 235-242. (d) Agami, C.; Couty, F.; Poursoulis, M. Synlett 1992, 847-848. (e) Bennett, D. J.; Hamilton, N. M. Tetrahedron Lett. 2000, 41, 7961-7964. (f) ref 4b.
20. For representative examples, see: (a) Overman, L. E.; Yokomatsu, T. J. Org. Chem. 1980, 45, 5229-5230. (b) Castelhano, A. L.; Krantz, A. J. Am. Chem. Soc. 1984, 106, 1877-1879. (c) Hart, D. J.; Yang, T.-K. J. Org. Chem. 1985, 50, 235-242. (d) Agami, C.; Couty, F.; Poursoulis, M. Synlett 1992, 847-848. (e) Bennett, D. J.; Hamilton, N. M. Tetrahedron Lett. 2000, 41, 7961-7964. (f) ref 4b.
21. For representative examples, see: (a) Overman, L. E.; Yokomatsu, T. J. Org. Chem. 1980, 45, 5229-5230. (b) Castelhano, A. L.; Krantz, A. J. Am. Chem. Soc. 1984, 106, 1877-1879. (c) Hart, D. J.; Yang, T.-K. J. Org. Chem. 1985, 50, 235-242. (d) Agami, C.; Couty, F.; Poursoulis, M. Synlett 1992, 847-848. (e) Bennett, D. J.; Hamilton, N. M. Tetrahedron Lett. 2000, 41, 7961-7964. (f) ref 4b.
22. For representative examples, see: (a) Overman, L. E.; Yokomatsu, T. J. Org. Chem. 1980, 45, 5229-5230. (b) Castelhano, A. L.; Krantz, A. J. Am. Chem. Soc. 1984, 106, 1877-1879. (c) Hart, D. J.; Yang, T.-K. J. Org. Chem. 1985, 50, 235-242. (d) Agami, C.; Couty, F.; Poursoulis, M. Synlett 1992, 847-848. (e) Bennett, D. J.; Hamilton, N. M. Tetrahedron Lett. 2000, 41, 7961-7964. (f) ref 4b.
23. 8 (Chemical Equation Presented)
24. Wavefunction, Inc.: Irvine, CA: 2002.
25. Usugi, S.; Yorimitsu, H.; Shinokubo, H.; Oshima, K. Bull. Chem. Soc. Jpn. 2002, 75, 2049-2052.
26. Cyclic aminoketals 12, 14, 18, 23, 26, and 29 were generated in a manner analogous to that of 10, whereas 16 and 20 were accessed by related routes; details are provided in Supporting Information.
27. These results contrast with the reaction of related aldehyde-derived iminium ions described in ref 6a, wherein the hydrolysis-directed reaction could be realized in the absence of dimedone.
28. 13
29. Aron, Z. D. Ph.D. Dissertation, University of California - Irvine, Irvine, CA, 2004; these details will be discussed in a future full account of this work.
30. At elevated reaction temperatures, dimedone decomposition was observed as a competitive process and sequential addition of this reagent over time was required to achieve useful yields in these cases.
31. Dimedone decomposes at elevated temperatures in the presence of ammonium salts, which is likely responsible for the incomplete deuterium incorporation observed in this experiment.