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Heck反应

 有机合成公众号 2020-11-03


钯催化下对烯烃进行烯基或芳基化的反应。另外不含β氢的卤代烃(主要是卤化苄)也可发生Heck反应,进行烷基化。

反应机理

首先卤代物进行氧化加成,然后对底物进行配位迁移,碳碳键旋转,二价钯和β氢进行顺位消除,还原消除催化剂循环。



反应实例


不对称分子间Heck反应。



还原Heck反应


参考文献

1. Heck, R. F.; Nolley, J. P., Jr. J. Am. Chem. Soc. 1968, 90, 5518-5526. Richard Heck discovered the Heck reaction when he was Hercules Corp. Heck won Nobel Prize in 2010 along with Akira Suzuki and Ei-ichi Negishi “for palladium-catalyzed cross couplings in organic synthesis”.  

2. Heck, R. F. Acc. Chem. Res. 1979, 12, 146-151. (Review).

3. Heck, R. F. Org. React. 1982, 27, 345-390. (Review).

4. Heck, R. F. Palladium Reagents in Organic Synthesis, Academic Press, London, 1985.(Book).

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9. Li, J. J. J. Org. Chem. 1999, 64, 8425-8427.

10. Beletskaya, I. P.; Cheprakov, A. V. Chem. Rev. 2000, 100, 3009-3066. (Review).

11. Amatore, C.; Jutand, A. Acc. Chem. Res. 2000, 33, 314-321. (Review).

12. Link, J. T. Org. React. 2002, 60, 157-534. (Review).

13. Lebsack, A. D.; Link, J. T.; Overman, L. E.; Stearns, B. A. J. Am. Chem. Soc. 2002, 124, 9008-9009.

14. Dounay, A. B.; Overman, L. E. Chem. Rev. 2003, 103, 2945-2963. (Review).

15. Beller, M.; Zapf, A.; Riermeier, T. H. Transition Metals for Organic Synthesis (2nd edn.) 2004, 1, 271-305. (Review).

16. Oestreich, M. Eur. J. Org. Chem. 2005, 783-792. (Review).

17. Baran, P. S.; Maimone, T. J.; Richter, J. M. Nature 2007, 446, 404-406.

18. Fuchter, M. J. Heck Reaction. In Name Reactions for Homologations-Part I; Li, J. J., Ed.; Wiley: Hoboken, NJ, 2009, pp 2-32. (Review).

19. The Mizoroki-Heck Reaction; Oestreich, M., Ed.; Wiley: Hoboken, NJ, 2009.

20. Bennasar, M.-L.; Solé, D.; Zulaica, E.; Alonso, S. Tetrahedron 2013, 69, 2534-2541.

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