Selective transformation of N-(propargylic)hydroxylamines into 4-isoxazolines and acylaziridines promoted by metal salts

Chemistry Letters

Volumn 40, Issue 5, 2011, Pages 440-442

  Wada, Norihiro ^a   Kaneko, Kentaro ^a   Ukaji, Yutaka ^a   Inomata, Katsuhiko ^a  

^a KANAZAWA UNIVERSITY   (Japan)

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EID: 79954576019     PISSN: 03667022     EISSN: 13480715     Source Type: Journal    
DOI: 10.1246/cl.2011.440     Document Type: Article

References (23)

1. J. P. Freeman, Chem. Rev. 1983, 83, 241
2. T. M. V. D. Pinho e Melo, Eur. J. Org. Chem. 2010, 3363.
3. a) E. J. Stoner, B. A. Roden, S. Chemburkar, Tetrahedron Lett. 1997, 38, 4981.
4. b) P. Aschwanden, D. E. Frantz, E. M. Carreira, Org. Lett. 2000, 2, 2331.
5. c) O. Debleds, C. D. Zotto, E. Vrancken, J.-M. Campagne, P. Retailleau, Adv. Synth. Catal. 2009, 351, 1991.
6. S.Pinet, S. U. Pandya, P. Y. Chavant, A. Ayling, Y. Vallee, Org. Lett. 2002, 4, 1463
7. F. Cantagrel, S. Pinet, Y. Gimbert, P. Y. Chavant, Eur. J. Org. Chem. 2005, 2694.
8. W.Wei, M. Kobayashi, Y. Ukaji, K. Inomata, Heterocycles 2009, 78, 717
9. Y. Ukaji, K. Inomata, Chem. Rec. 2010, 10, 173.
10. a)J.E.Baldwin, R. G. Pudussery, A. K. Qureshi, B. Sklarz, J. Am. Chem. Soc. 1968, 90, 5325
11. b) I. Adachi, R. Miyazaki, H. Kano, Chem. Pharm. Bull. 1974, 22, 70.
12. c) R. Grée, R. Carrié, J. Am. Chem. Soc. 1977, 99, 6667.
13. c) G. Chidichimo, G. Cum, F. Lelj, G. Sindona, N. Uccella, J. Am. Chem. Soc. 1980, 102, 1372.
14. e) K. Tanaka, M. Ohsuga, Y. Sugimoto, Y. Okafuji, K. Mitsuhashi, J. Fluorine Chem. 1988, 39, 39.
15. f) T. Ishikawa, T. Kudoh, J. Yoshida, A. Yasuhara, S. Manabe, S. Saito, Org. Lett. 2002, 4, 1907.
16. g) B. Alcaide, P. Almendros, J. M. Alonso, M. F. Aly, C. Pardo, E. Sáez, M. R. Torres, J. Org. Chem. 2002, 67, 7004.
17. h) E. M. Budynina, E. B. Averina, O. A. Ivanova, T. S. Kuznetsova, N. S. Zefirov, Tetrahedron Lett. 2005, 46, 657.
18. i) E. Gayon, O. Debleds, M. Nicouleau, F. Lamaty, A. Lee, E. Vrancken, J.-M. Campagne, J. Org. Chem. 2010, 75, 6050.
19. The cis-stereochemistry of 3a3f was confirmed by the coupling constant J23 (6.47.4 Hz) between the methane protons in aziridine rings.5
20. A previous report which excluded the possibility of a radical pathway based on a controlled experiment using galvinoxyl free radical: Y. Kuninobu, H. Ueda, A. Kawata, K. Takai, J. Org. Chem. 2007, 72, 6749.
21. When 2a was treated with 1.0 equiv of CuOTf(C6H6)0.5 in ClCH2CH6Cl at 80 °C for 0.5 h, 3a was obtained in 80% yield and diastereoselectivity was still high (3a/transisomer = 20/1, determined by 1HNMR spectrum of the crude products) different from the result of the similar reaction promoted by Co2 (CO) 8 (0.5 equiv), in which cis/ trans isomers' ratio was 2.8/1.5f This fact might suggest that the present reaction does not proceed through a radical pathway via the metal enolateaza radical intermediate as proposed in ref. 5f.
22. When the direct transformation of 1a to 3a according to Entry 10 in Table 2 was performed in the presence of galvinoxyl free radical (1.2 equiv), the reaction proceeded sluggishly to give 3a in 10% yield accompanied by the production of an imine, N-(1,3-diphenylprop-2-ylidene)- benzylamine (41) (34%). Galvinoxyl free radical might oxidize CuCl to give more Lewis acidic Cu(I10) species, which promoted the dehydration of 1a.
23. Aziridines; for example: G. Cardillo, L. Gentilucci, A. Tolomelli, Aldrichimica Acta 2003, 36, 39, and references cited therein.