【Catellani, M.; Frignani, F.; Rangoni, A. Angew. Chem. Int. Ed. Engl. 1997, 36,119–122.】
在降冰片烯(Norbornene)与Pd共同催化作用下,芳基碘化物先和降冰片烯进行Heck反应,接着邻位C-H活化进行烷基化或芳基化的反应,最后再和端基烯烃偶联得到邻位取代的烯基芳烃的反应。此反应是三组分偶联反应。邻位单取代的芳基碘化物作为底物则可以得到不同邻位取代基的烯基芳烃。
1997年意大利化学家Catellani首次报道了此反应,因此也由其名字命名。
反应机理
Pd在催化循环中分别经历了0・II・IV价态。在苯环邻位C-H活化阶段,首先是反应性较高的降冰片烯进行插入,拉近了Pd与邻位C-H的距离后完成的整个催化循环。最近计算化学再次验证解释了其具体反应机理(Catellani M. et al, J. Am. Chem. Soc. 2011, 133, 8574. DOI:10.1021/ja110988p )
反应实例
【(a) Lautens, M.; Piguel, S.; Dahlmann, M. Angew. Chem. Int. Ed. Engl. 2000, 39, 1045–1046. (b) Lautens, M.; Paquin, J.-F.; Piguel, S. J. Org. Chem. 2001, 66, 8127–8134. (c) Lautens, M.; Paquin, J.-F.; Piguel, S. J. Org. Chem. 2002, 67, 3972–3974.】
【Angew. Chem. Int. Ed. 2013, 125, 5413–5416】
【Synthesis 2003, 2671–2678】
【J. Am. Chem. Soc. 2004, 126, 78–79.】
【Angew. Chem. Int. Ed. 2011, 50, 6896–6899;
Angew. Chem. Int. Ed. 2011, 50, 12257–12261.】
相关文献
1. (a) Tsuji, J. Palladium Reagents and Catalysts – New Perspective for the 21st Century,2004, John Wiley & Sons, pp. 409–416. (b) Catellani, M. Synlett 2003, 298–313. (c) Catellani, M. Top. Organomet. Chem. 2005, 14, 21–53. (d) Catellani M.; Motti E.; Della Ca’ N. Acc. Chem. Res. 2008, 41, 1512–1522. (e) Martins, A.; Mariampillai, B.; Lautens, M. Top Curr Chem 2010, 292, 1–33. (f) Chiusoli, G. P.; Catellani, M.; Costa, M.; Motti, E.; Della Ca’, N.; Maestri, G. Coord. Chem. Rev. 2010, 254, 456–469.
2. (a) Catellani, M.; Frignani, F.; Rangoni, A. Angew. Chem. Int. Ed. Engl. 1997, 36,
119–122. (b) Catellani, M.; Fagnola, M. C. Angew. Chem. Int. Ed. Engl. 1994, 33,2421–2422.
3. Catellani, M;. Cugini, F. Tetrahedron, 1999, 55, 6595–6602.
4. (a) Lautens, M.; Piguel, S.; Dahlmann, M. Angew. Chem. Int. Ed. Engl. 2000, 39,
1045–1046. (b) Lautens, M.; Paquin, J.-F.; Piguel, S. J. Org. Chem. 2001, 66, 8127–8134. (c) Lautens, M.; Paquin, J.-F.; Piguel, S. J. Org. Chem. 2002, 67, 3972–3974.
5. Weinstabl, H.; Suhartono, M.; Qureshi, Z.; Lautens, M. Angew. Chem. Int. Ed. 2013,125, 5413–5416.
6. Maestri, G.; Motti, E.; Della Ca’, N.; Malacria, M.; Derat, E.; Catellani, M. J. Am. Chem. Soc. 2011, 133, 8574–8585.
7. Motti, E.; Ippomei, G.; Deledda, S.; Catellani, M. Synthesis 2003, 2671–2678.
8. Faccini, F.; Motti, E.; Catellani, M. J. Am. Chem. Soc. 2004, 126, 78-79.
9. Vicente, J.; Arcas, A.; Juliá-Hernández, F.; Bautista, D. Angew. Chem. Int. Ed. 2011,50, 6896–6899.
10. Della Ca’, N.; Maestri, G.; Malacria, M.; Derat, E.; Catellani, M. Angew. Chem. Int. Ed. 2011, 50, 12257–12261.
编译自:J.J. Li, Name Reactions: A Collection of Detailed Mechanisms and Synthetic Applications, Catellani reaction,page 112-114.