Room temperature hydroalkylation of electron-deficient olefins: sp 3 C-H functionalization via a Lewis acid-catalyzed intramolecular redox event

Journal of the American Chemical Society

Volumn 127, Issue 35, 2005, Pages 12180-12181

  Pastine, Stefan J ^a   McQuaid, Kevin M ^a   Sames, Dalibor ^a  

^a Och Spine at New York Presbyterian Hospitals   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; CARBON; HYDROGEN; LEWIS ACID;

ALKYLATION; ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; CYCLIZATION; ELECTRON; HYDROXYLATION; OXIDATION REDUCTION REACTION; ROOM TEMPERATURE;

ACIDS; ALKENES; ALKYLATION; CARBON; CATALYSIS; ELECTRONS; HYDROGEN; MODELS, CHEMICAL; OXIDATION-REDUCTION; TEMPERATURE;

EID: 24644495100     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja053337f     Document Type: Article

References (24)

1. (a) Chatani, N.; Asaumi, T.; Yorimitsu, S.; Ikeda, T.; Kakiuchi, F.; Murai, S. J. Am. Chem. Soc. 2001, 123, 10935 and references therein.
2. (b) Sakakura, T.; Abe, F.; Tanaka, M. Chem. Lett. 1991, 359.
3. (c) Lin, Y.; Ma, D.; Lu, X. Tetrahedron Lett. 1987, 28, 3249.
4. DeBoef, B.; Pastine, S. J.; Sames, D. J. Am. Chem. Soc. 2004, 126, 6556.
5. Although the mechanism in these reports is suggested to proceed through a 1,5-sigmatropic hydrogen shift, it is possible that a direct hydride transfer mechanism is operative. Selected examples: (a) Noguchi, M.; Yamada, H.; Sunagawa, T. J. Chem. Soc., Perkin Trans. 1 1998, 3327.
6. (b) Nijhuis, W. H. N.; Verboom, W.; El-Fadl, A. A.; Harkema, S.; Reinhoudt, D. N. J. Org. Chem. 1989, 54, 199.
7. (c) Nijhuis, W. H. N.; Verboom, W.; Reinhoudt, D. N. J. Am. Chem. Soc. 1987, 109, 3136.
8. (d) Nijhuis, W. H. N.; Verboom, W.; Reinhoudt, D. N. Synthesis 1987, 641.
9. Mayr, H.; Kempf, B.; Ofial, A. R. Acc. Chem. Res. 2003, 36, 66.
10. The term "through space" is used to differentiate this process from more common hydride shifts that proceed through a σ- or π-framework. The overwhelming majority of these examples proceed through a six-membered transition state. For selected examples, see: (a) Kanischev, M. I.; Schegolev, A. A.; Smit, W. A.; Caple, R.; Keiner, M. J. J. Am. Chem. Soc. 1979, 101, 5660 and references therein,
11. (b) Schulz, J. G. D.; Onopchenko, A. J. Org. Chem. 1978, 43, 339.
12. (c) Heathcock, C. H.; Piettre, S.; Ruggeri, R. B.; Ragan, J.; Kath, J. C. J. Org. Chem. 1992, 57, 2544.
13. (d) Krohn, K.; Flörke, U.; Höfker, U.; Träubel, M. Eur. J. Org. Chem. 1999, 3495.
14. (e) Wölfling, J.; Frank, E.; Schneider, G.; Tietze, L. F. Angew. Chem., Int. Ed. 1998, 38, 200.
15. (f) Diaz, D.; Martín, V. S. Org. Lett. 2000, 2, 335.
16. (g) Diaz, D.; Martín, V. S. Tetrahedron Lett. 2000, 41, 743.
17. (h) Wölfling, J.; Frank, E.; Schneider, G.; Tietze, L. F. Eur. J. Org. Chem. 2004, 90.
18. A byproduct stemming from the opening of the spiro-system formed in this reaction (see the Supporting Information).
19. (a) Pastine, S. J.; Youn, S. W.; Sames, D. Org. Lett. 2003, 5, 1055.
20. (b) Pastine, S. J.; Youn, S. W.; Sames, D. Tetrahedron 2003, 59, 8859.
21. The relative amount of 14a and 14b is dependent on the reaction time and the catalyst employed.
22. Inoue, H.; Chatani, N.; Murai, S. J. Org. Chem. 2002, 67, 1414.
23. For oxidative intermolecular C-C bond formation at the α-position of reactive amines, see: (a) Murahashi, S.-I.; Komiya, N.; Terai, H.; Nakae, T. J. Am. Chem. Soc. 2003, 125, 15312.
24. (b) Li, Z.; Li, C.-J. J. Am. Chem. Soc. 2005, 127, 6968 and references therein.