【Catellani, M.; Frignani, F.; Rangoni, A. Angew. Chem. Int. Ed. Engl. 1997, 36,119–122.】
在降冰片烯(Norbornene)與Pd共同催化作用下，芳基碘化物先和降冰片烯進(jìn)行Heck反應(yīng)，接著鄰位C-H活化進(jìn)行烷基化或芳基化的反應(yīng)，最后再和端基烯烴偶聯(lián)得到鄰位取代的烯基芳烴的反應(yīng)。此反應(yīng)是三組分偶聯(lián)反應(yīng)。鄰位單取代的芳基碘化物作為底物則可以得到不同鄰位取代基的烯基芳烴。
1997年意大利化學(xué)家Catellani首次報(bào)道了此反應(yīng)，因此也由其名字命名。
反應(yīng)機(jī)理
Pd在催化循環(huán)中分別經(jīng)歷了0?II?IV價(jià)態(tài)。在苯環(huán)鄰位C-H活化階段，首先是反應(yīng)性較高的降冰片烯進(jìn)行插入，拉近了Pd與鄰位C-H的距離后完成的整個(gè)催化循環(huán)。最近計(jì)算化學(xué)再次驗(yàn)證解釋了其具體反應(yīng)機(jī)理（Catellani M. et al, J. Am. Chem. Soc. 2011, 133, 8574. DOI:10.1021/ja110988p ）
反應(yīng)實(shí)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.】
相關(guān)文獻(xiàn)
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.
編譯自：J.J. Li, Name Reactions: A Collection of Detailed Mechanisms and Synthetic Applications, Catellani reaction，page 112-114.
