Cycloaddition/ring opening of 3-unsubstituted cyclic nitronates, isoxazoline and 5,6-dihydro-4H-1,2-oxazine N-oxides, as synthetic equivalents of functionalized nitrile oxides

Tetrahedron Letters

Volumn 39, Issue 48, 1998, Pages 8869-8872

  Kanemasa, Shuji ^a   Yoshimiya, Takanori ^a   Wada, Eiji ^a  

^a KYUSHU UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ETHYLENE; ISOXAZOLINE DERIVATIVE; NITRILE; NITROALKANE;

ARTICLE; CHEMICAL REACTION; CYCLIZATION; REACTION ANALYSIS; STRUCTURE ANALYSIS;

EID: 0032569821     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)01903-0     Document Type: Article

References (25)

1. 1. (a) Torssell, K. B. G.; Hazell, A. C.; Hazell, R. G. Tetrahedron 1985, 41, 5569-5576.
2. (b) Tartakovskii, V. A.; Savost'yanova, I. A.; Novikov, S. S. Zh. Org. Khim., 1968, 4, 240-243.
3. (c) Boron trifluoride catalyzes the cycloaddition of nitronic esters: Levina, I. S.; Mortikova, E. I.; Kamernitzky, A. V. Synthesis, 1974, 562-563.
4. 2. Wade, P. A.; Amin, N. V.; Yen, H.-K.; Price, D. T.; Huhn, G. F. J. Org. Chem, 1984, 49, 4595-4601.
5. 3. Reviews: (a) Kamimura, A. J. Syn. Org. Synth., Jpn. 1992, 50, 808-825.
6. (2) Kanemasa, S.; Tsuge, O. Heterocycles, 1990, 30, 719-736.
7. (c) Curran, D. P. Advances in Cycloaddition; Curran, D. P., Ed.; JAI Press: Greenwich, 1988; Vol. 1, pp 129-189.
8. 4. (a) Wade, P. A.; Hinney, H. R. J. Am. Chem. Soc. 1979, 101, 1319-1320 (sulphonyl).
9. (b) Kozikowski, A. P.; Ghosh, A. K. Tetrahedron Lett. 1983, 24, 2623-2626 (hydroxymethyl).
10. (c) Tsuge, O.; Kanemasa, S.; Suga, H. Chem. Lett. 1986, 183-186 (phosphorylmethyl).
11. (d) Jäger, V.; Müller, I. Tetrahedron, 1985, 41, 3519-3528 (alkoxyl and acetal).
12. (e) Kozikowski, A. P.; Li, C-S. J. Org. Chem. 1985, 50, 778-785 (acetal).
13. 5. Catalyzed asymmetric nitrone cycloadditions, see the references cited in Ref. 6.
14. 6. Kanemasa, S.; Kaga, S.; Wada, E. Submitted to this journal.
15. 7. Denmark. S. E.; Thorarensen, A. Chem. Rev. 1996, 96, 137-165.
16. 8. In situ generation of 3-unsubstituted cyclic nitronates has been reported (Tartakovskii, V. A.; Chlenov, I. E.; Smagin, S. S.; Novikov, S. S. Izv. Akad. Nauk SSSR Ser. Khim. 1964, 583-584).
17. 9. 3-Chloro-1-nitropropane (1, X = Cl) and 4-chloro-1-nitrobutane (10, X = Cl) are less reactive starting materials because cyclization of the nitronate anions is very slow. Yields of 5, 12, 13 are always less than 10% and the starting chloro compounds 1 and 10 are mostly recovered unchanged.
18. 10. When 1 (X = I) was treated with triethylamine (2 equiv) and methyl acrylate (1.2 equiv) at rt in dichloromethane, the corresponding isoxazoline was produced in 17% yield.
19. 11. During the separation procedure by column chromatography on silica gel, most of 2 decomposes.
20. 12. Similar thermal or base induced β-elimination leading to β-hydroxy nitriles is known: (a) Christl, M.; Mattauch, B.; Irngartinger, H.; Goldmann, A. Chem. Ber. 1986, 119, 950-959.
21. (b) Das, N. B.; Torssell, K. B. G.; Tetrahedron, 1983, 39, 2247-2253.
22. (c) De Sarlo, F.; Brandi, A.; Goti, A.; Guarna, A.; Rovero, P. Heterocycles, 1983, 20, 511-518,
23. (d) Kozikowski, A. P.; Ghosh, A. K.; J. Am. Chem. Soc. 1982, 104, 5788-5789.
24. 13. After the reaction was complete, the dichloromethane was concentrated in vacuo at rt. Hexane was added and the precipitate was removed by filteration. The filtrate was evaporated in vacuo to give the residue which contained almost pure 11. The nitronate 11 may be stored for weeks in a freezer and one week in deuteriochloroform at rt.
25. d) to be identified as 4a,4b-cis-isomer (endo-isomer).