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Favorskii重排2019-03-21

可以烯醇化的α-卤代酮在烷氧基,羟基或胺催化下重排分别生成酯,羧酸或酰胺的反应。


环状底物的Favorskii重排


反应机理

烯醇化的α-卤代酮进行分子内的SN2反应得到环丙酮中间体,亲核试剂进攻环丙酮的羰基进行重排生成产物。

反应实例






参考文献

1. (a) Favorskii, A. E. J. Prakt. Chem. 1895, 51, 533563. Aleksei E. Favorskii

(1860-1945), born in Selo Pavlova, Russia, studied at St. Petersburg State University, where he became a professor since 1900. (b) Favorskii, A. E. J. Prakt. Chem. 1913,88, 658.

2. Wagner, R. B.; Moore, J. A. J. Am. Chem. Soc. 1950, 72, 3655 3658.

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6. White, J. D.; Dillon, M. P.; Butlin, R. J. J. Am. Chem. Soc. 1992, 114, 9673 9674.

7. Dhavale, D. D.; Mali, V. P.; Sudrik, S. G.; Sonawane, H. R. Tetrahedron 1997, 53,16789 16794.

8. Kitayama, T.; Okamoto, T. J. Org. Chem. 1999, 64, 2667 2672.

9. Mamedov, V. A.; Tsuboi, S.; Mustakimova, L. V.; Hamamoto, H.; Gubaidullin, A. T.;Litvinov, I. A.; Levin, Y. A. Chem. Heterocyclic Compd. 2001, 36, 911. (Review).

10. Harmata, M.; Wacharasindhu, S. Org. Lett. 2005, 7, 2563 2565.

11. Pogrebnoi, S.; Saraber, F. C. E.; Jansen, B. J. M.; de Groot, A. Tetrahedron 2006, 62,1743 1748.

12. Filipski, K.J.; Pfefferkorn, J. A. Favorskii Rearrangement. In Name Reactions forHomologations-Part II; Li, J. J., Ed.; Wiley: Hoboken, NJ, 2009, pp 238252. (Review).

13. Kammath, V. B.; Šolomek, T.; Ngoy, B. P.; Heger, D.; Klán, P.; Rubina, M.; Givens,R. S. J. Org. Chem. 2013, 78, 1718–1729.

 

编译自:J.J. Li, Name Reactions: A Collection of Detailed Mechanisms and Synthetic Applications, Favorskii rearrangement7page 239-241.

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