Skeletal rearrangements in the 2,3-diazanorbornene series. A fast access to highly functionalized cyclopentanes

Organic Letters

Volumn 8, Issue 14, 2006, Pages 3041-3043

  Bournaud, Chloée ^a   Bonin, Martine ^a   Micouin, Laurent ^a  

^a UNIVERSITÉ PARIS DESCARTES   (France)

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Indexed keywords

EID: 33746603087     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol060972x     Document Type: Article

References (25)

1. Pale, P.; Vogel, P. In Comprehensive Organic Functional Group Transformations 2; Katritzky, A. R., Taylor, R. J. K., Eds.; Elsevier: Amsterdam, 2005; Vol. 1, p 889.
2. Malpass, J. R.; White, R. J. Org. Chem. 2004, 69, 5328 and references cited therein.
3. (a) Pérez Luna, A.; Ceschi, M.-A.; Bonin, M.; Micouin, L.; Husson, H.-P.; Gougeon, S.; Estenne-Bouhtou, G.; Marabout, B.; Sevrin, M.; George, P. J. Org. Chem. 2002, 67, 3522.
4. (b) Pérez Luna, A.; Bonin, M.; Micouin, L.; Husson, H.-P. J. Am. Chem. Soc. 2002, 124, 12098.
5. (c) Pérez Luna, A.; Cesario, M.; Bonin, M.; Micouin, L. Org. Lett. 2003, 5, 4771.
6. Bournaud, C.; Robic, D.; Bonin, M.; Micouin, L. J. Org. Chem. 2005, 70, 3316.
7. Reviews: (a) Cossy, J.; Gomez Pardo, D. Targets Heterocycl. Syst. 2002, 6, 1.
8. (b) Dahanukar, V. H.; Zavialov, L. A. Curr. Opin. Drug. Discovery Dev. 2002, 5, 918.
9. For a NMR description of aziridinium imide, see: Poon, T. H. W.; Park, S. H.; Elemes, Y.; Foote, C. S. J. Am. Chem. Soc. 1995, 117, 10468.
10. The bromination of diazanorbornenes has been described to occur with nitrogen participation and rearrangement in a seminal study: Raasch, M. S. J. Org. Chem. 1975, 40, 161.
11. (a) Winstein, S.; Trifan, D. S. J. Am. Chem. Soc. 1949, 71, 2953.
12. (b) Winstein, S.; Trifan, D. S. J. Am. Chem. Soc. 1952, 74, 1147.
13. (c) Winstein, S.; Trifan, D. S. J. Am. Chem. Soc. 1952, 74, 1154.
14. (d) For a general discussion on norbornyl cations, see: Olah, G. A. Acc. Chem. Res. 1976, 9, 41.
15. Enantiomerically enriched 9 was prepared by a reported procedure: see ref 3a.
16. Mitsunobu, O. Synthesis 1981, 1.
17. Nucleophilic substitutions with retention of configuration under Mitsunobu conditions involving aziridinium species are precedented. See for example: Freedman, J.; Vall, M. J.; Huber, E. W. J. Org. Chem. 1991, 56, 670.
18. For a rearrangement triggered by a Mitsunobu reaction, see: Dondoni, A.; Richichi, B.; Marra, A.; Perrone, D. Synlett 2004, 1711.
19. The solvolysis of brosylate 7 has been described to occur with complete racemization, whereas only partial epimerization was observed in our experiments. The partial retention of configuration could tentatively be explained by the formation of a meso, but not fully symmetrical, distorted aziridinium intermediate having unequal bond lengths and leading to the preferential attack of the nucleophile on the carbon that bared the leaving group. We observed that the enantiomeric ratio of the substituted hydrazine 11 was not solvent (THF, toluene) nor temperature (rt to 110 °C) dependent.
20. Walborsky, H. M.; Loncrini, D. F. J. Org. Chem. 1957, 22, 1117.
21. Allred, E. L.; Anderson, C. L.; Smith, R. L. J. Org. Chem. 1966, 31, 3493.
22. 4; the solvent was evaporated, and the crude was purified by silica gel chromatography (elution conditions: cyclohexane/ethyl acetate 80:20) to give 5f as a yellow oil (160 mg, 0.33 mmol). The alane solution was prepared according to our previously reported procedure: Feuvrie, C.; Blanchet, J.; Bonin, M.; Micouin, L. Org. Lett. 2004, 6, 2333.
23. For an excellent review on the use of trifluoroethanol as a solvent in cationic rearrangements, see: Bégué, J.-P.; Bonnet-Delpon, D.; Crousse, B. Synlett 2004, 18.
24. Acid-catalyzed aziridinium generation from 2,3-epoxy amines has been described: Liu, Q.; Marchington, A. P.; Rayner, C. M. Tetrahedron 1997, 53, 15729.
25. The reaction of organoaluminum reagents with 2,3-epoxy amines has been described to involve aziridinium intermediates, leading to a C-2 ring-opened product with retention of configuration: Liu, C.; Hashimoto, Y.; Saigo, K. Tetrahedron Lett. 1996, 37, 6177.