Does the facile reductive rearrangement of 2-allyloxycyclohexenone with Bu3SnH occur by a radical-accelerated Claisen rearrangement or a stannyloxy- accelerated Claisen rearrangement? [8]

Journal of the American Chemical Society

Volumn 121, Issue 38, 1999, Pages 8955-8956

  Curran, Dennis P ^a   Nishii, Yoshinori ^a  

^a UNIVERSITY OF PITTSBURGH   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

2 CYCLOHEXENONE DERIVATIVE; ANION; RADICAL; SILANE DERIVATIVE; TIN DERIVATIVE;

CONFORMATION; DIASTEREOISOMER; HYDROLYSIS; LETTER; NUCLEAR OVERHAUSER EFFECT; REACTION ANALYSIS; REDUCTION; STEREOCHEMISTRY; STEREOISOMERISM;

EID: 0033615303     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja991663n     Document Type: Letter

References (23)

1. Bronson, J. J.; Danheiser, R. L. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 5, p 999. Wipf, P. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 5, p 827. Gajewski, J. J. Acc. Chem. Res. 1997, 30, 219.
2. Bronson, J. J.; Danheiser, R. L. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 5, p 999. Wipf, P. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 5, p 827. Gajewski, J. J. Acc. Chem. Res. 1997, 30, 219.
3. Bronson, J. J.; Danheiser, R. L. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 5, p 999. Wipf, P. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, 1991; Vol. 5, p 827. Gajewski, J. J. Acc. Chem. Res. 1997, 30, 219.
4. However, radicals and radical ions are frequently postulated as intermediates (as opposed to substituents). See, for example: Bauld, N. L. In Advances in Electron-Transfer Chemistry; Mariano, P. S., Ed.; Jai Press Inc.: Greenwich, CT, 1992; Vol. 2, p 1.
5. (a) Zhang, X. M. J. Org. Chem. 1998, 63, 1872.
6. (b) Zhao, Y. Y.; Bordwell, F. G. J. Org. Chem. 1996, 61, 6623.
7. Enholm, E. J.; Moran, K. M.; Whitley, P. E.; Battiste, M. A. J. Am. Chem. Soc. 1998, 120, 3807.
8. 10; see Supporting Information.
9. Koreeda, M.; Luengo, J. I. J. Am. Chem. Soc. 1985, 107, 5573. For a recent application of this type of rearrangement, see: Wood, J. L.; Moniz, G. A.; Pflum, D. A.; Stolz, B. M.; Holubec, A. A.; Dietrich, H.-J. J. Am. Chem. Soc. 1999, 121, 1748.
10. Koreeda, M.; Luengo, J. I. J. Am. Chem. Soc. 1985, 107, 5573. For a recent application of this type of rearrangement, see: Wood, J. L.; Moniz, G. A.; Pflum, D. A.; Stolz, B. M.; Holubec, A. A.; Dietrich, H.-J. J. Am. Chem. Soc. 1999, 121, 1748.
11. Enholm, E. J.; Xie, Y. P.; Abboud, K. A. J. Org. Chem. 1995, 60, 1112. Enholm, E. J.; Whitley, P. E. Tetrahedron Lett. 1995, 36, 9157. Enholm, E. J.; Whitley, P. E. Tetrahedron Lett. 1996, 37, 559. Enholm, E. J.; Whitley, P. E.; Xie, Y. P. J. Org. Chem. 1996, 61, 5384.
12. Enholm, E. J.; Xie, Y. P.; Abboud, K. A. J. Org. Chem. 1995, 60, 1112. Enholm, E. J.; Whitley, P. E. Tetrahedron Lett. 1995, 36, 9157. Enholm, E. J.; Whitley, P. E. Tetrahedron Lett. 1996, 37, 559. Enholm, E. J.; Whitley, P. E.; Xie, Y. P. J. Org. Chem. 1996, 61, 5384.
13. Enholm, E. J.; Xie, Y. P.; Abboud, K. A. J. Org. Chem. 1995, 60, 1112. Enholm, E. J.; Whitley, P. E. Tetrahedron Lett. 1995, 36, 9157. Enholm, E. J.; Whitley, P. E. Tetrahedron Lett. 1996, 37, 559. Enholm, E. J.; Whitley, P. E.; Xie, Y. P. J. Org. Chem. 1996, 61, 5384.
14. Enholm, E. J.; Xie, Y. P.; Abboud, K. A. J. Org. Chem. 1995, 60, 1112. Enholm, E. J.; Whitley, P. E. Tetrahedron Lett. 1995, 36, 9157. Enholm, E. J.; Whitley, P. E. Tetrahedron Lett. 1996, 37, 559. Enholm, E. J.; Whitley, P. E.; Xie, Y. P. J. Org. Chem. 1996, 61, 5384.
15. See Supporting Information for an evaluation of these experiments.
16. Curran, D. P.; Porter, N. A.; Giese, B. Stereochemistry of Radical Reactions: Concepts, Guidelines, and Synthetic Applications; VCH: Weinheim, 1996; p 283.
17. We choose to model the stannyl ether group with a silyl ether because stannyl ethers are hydrolytically sensitive and are difficult to form from tertiary alcohols. See: Davies, A. G. Organotin Chemistry; VCH: Weinheim, 1997; p 327. After many failures, the tin ether from 9 was ultimately generated in situ (see text). That it provides the same results as the silyl ether and alcohol supports the validity of this model.
18. Jones, K.; Lappert, M. F. J. Chem. Soc. 1965, 1944.
19. For representative examples where the rates of radical reactions exceed those of relatively rapid conformation processes, see: (a) Snieckus, V.; Cuevas, J. C.; Sloan, C. P.; Liu, H.; Curran, D. P. J. Am. Chem. Soc. 1990, 112, 896. (b) Sauer, S.; Schumacher, A.; Barbosa, F.; Giese, B. Tetrahedron Lett. 1998, 39, 3685. (c) Buckmelter, A. J.; Powers, J. P.; Rychnovsky, S. D. J. Am. Chem. Soc. 1998, 120, 5589. (d) Musa, O. M.; Homer, J. H.; Newcomb, M. J. Org. Chem. 1999, 64, 1022.
20. For representative examples where the rates of radical reactions exceed those of relatively rapid conformation processes, see: (a) Snieckus, V.; Cuevas, J. C.; Sloan, C. P.; Liu, H.; Curran, D. P. J. Am. Chem. Soc. 1990, 112, 896. (b) Sauer, S.; Schumacher, A.; Barbosa, F.; Giese, B. Tetrahedron Lett. 1998, 39, 3685. (c) Buckmelter, A. J.; Powers, J. P.; Rychnovsky, S. D. J. Am. Chem. Soc. 1998, 120, 5589. (d) Musa, O. M.; Homer, J. H.; Newcomb, M. J. Org. Chem. 1999, 64, 1022.
21. For representative examples where the rates of radical reactions exceed those of relatively rapid conformation processes, see: (a) Snieckus, V.; Cuevas, J. C.; Sloan, C. P.; Liu, H.; Curran, D. P. J. Am. Chem. Soc. 1990, 112, 896. (b) Sauer, S.; Schumacher, A.; Barbosa, F.; Giese, B. Tetrahedron Lett. 1998, 39, 3685. (c) Buckmelter, A. J.; Powers, J. P.; Rychnovsky, S. D. J. Am. Chem. Soc. 1998, 120, 5589. (d) Musa, O. M.; Homer, J. H.; Newcomb, M. J. Org. Chem. 1999, 64, 1022.
22. For representative examples where the rates of radical reactions exceed those of relatively rapid conformation processes, see: (a) Snieckus, V.; Cuevas, J. C.; Sloan, C. P.; Liu, H.; Curran, D. P. J. Am. Chem. Soc. 1990, 112, 896. (b) Sauer, S.; Schumacher, A.; Barbosa, F.; Giese, B. Tetrahedron Lett. 1998, 39, 3685. (c) Buckmelter, A. J.; Powers, J. P.; Rychnovsky, S. D. J. Am. Chem. Soc. 1998, 120, 5589. (d) Musa, O. M.; Homer, J. H.; Newcomb, M. J. Org. Chem. 1999, 64, 1022.
23. It was also reported that reductive rearrangement of 2-allyloxy-3-methylcyclohexenone provided the opposite stereosiomer, as would be expected from both the Enholm and Koreeda mechanisms.