Chan–Lam C–X偶聯反應

舊文重發,溫故知新

含有NH/OH/SH基團的底物在弱鹼條件下,在空氣中通過醋酸銅催化,與有機硼酸化合物氧化交叉偶聯進行芳基,烯基和烷基化的反應。

常見的反應底物:醯胺,胺,脒,苯胺類,疊氮化物,唑類,乙內醯脲類,肼類,醯亞胺,亞胺,亞硝基化合物,吡嗪酮,嘌呤,嘧啶,磺醯胺類,亞磺酸胺,亞磺醯亞胺,脲,醇,酚,硫醇等等。硼酸也可以被其他活性化合物代替:矽氧烷,錫烷,和其他有機金屬化合物。此反應比Buchwald–Hartwig鈀催化反應的優點就是條件比較溫和,但是原料硼酸比Buchwald–Hartwig的原料芳滷要貴。

ChanLam C–X偶聯反應在有機合成中與非常類似的Suzuki–Miyaura’s C–C 交叉偶聯反應一樣應用非常廣泛。

反應機理

硼酸和催化劑進行絡合,金屬轉移(不可逆過程),二價銅絡合物被氧化為三價銅絡合物,與胺反應還原消除得到產物,生成的一價銅被氧氣氧化完成催化劑迴圈。

反應例項

Dominic Chanis a chemist at DuPont Crop Protection, Wilming ton, DE, USA. He did his PhD research with Prof. Barry Trost at the University of Wisconson, Madison.

Patrick Lamis a research director at Bristol–Myers Squibb, Princeton, NJ, USA. He was formerly with DuPont Pharmaceuticals Company. He did his PhD research with Prof. Louis Friedrich in the Univeristy of Rochester and Post-doc research with Prof. Michael Jung and the late Prof. Donald Cram in UCLA.

Prof. Evans’ group found out about the discovery of this reaction on a National organic Symposium poster and be came interested in the O-arylation because of his long interest in vancomycin total synthesis.

參考文獻

1. (a) Chan, D. M. T.; Monaco, K. L.; Wang, R.-P.; Winters, M. P. Tetrahedron Lett. 1998, 39, 2933-2936. (b) Lam, P. Y. S.; Clark, C. G.; Saubern, S.; Adams, J.; Winters, M. P.; Chan, D. M. T.; Combs, A. Tetrahedron Lett. 1998, 39, 2941-2949. (c) Evans, D. A.; Katz, J. L.; West, T. R. Tetrahedron Lett. 1998, 39, 2937-2940. (d) Lam, P. Y. S.; Clark, C. G.; Saubern, S.; Adams, J.; Averill, K. M.; Chan, D. M. T.; Combs, A. Synlett 2000, 674-676. (e) Lam, P. Y. S.; Bonne, D.; Vincent, G.; Clark, C. G.; Combs, A. P. Tetrahedron Lett. 2003, 44, 1691-1694.

2. Reviews: (a) Qiao, J. X.; Lam, P. Y. S. Syn. 2011, 829-856; (b) Chan, D. M. T.; Lam, P. Y. S., Book chapter in Boronic Acids Hall, ed. 2005, Wiley–VCH, 205– 240. (c) Ley, S. V.; Thomas, A. W. Angew. Chem., Int. Ed. Engl. 2003, 42, 5400–5449.

3. Catalytic copper: (a) Lam, P. Y. S.; Vincent, G.; Clark, C. G.; Deudon, S.;Jadhav, P. K. Tetrahedron Lett. 2001, 42, 3415-3418. (b) Antilla, J. C.; Buchwald, S. L. Org. Lett. 2001, 3, 2077-2079. (c) Quach, T. D.; Batey, R. A. Org.Lett. 2003, 5, 4397-4400. (d) Collman, J. P.; Zhong, M. Org. Lett. 2000, 2,1233-1236. (e) Lan, J.-B.; Zhang, G.-L.; Yu, X.-Q.; You, J.-S.; Chen, L.; Yan,M.; Xie, R.-G. Synlett 2004, 1095-1097.

4. Mechanism (Part of the mechanistic work from Shannon’s lab was funded and in collaboration with BMS: (a) Huffman, L. M.; Stahl, S. S. J. Am. Chem. Soc. 2008, 130, 9196-9197. (b) King, A. E.; Brunold, T. C.; Stahl, S. S. J. Am. Chem. Soc.2009, 131, 5044. (c) King, A. E.; Huffman, L. M.; Casitas, A.; Costas, M.; Ribas,

X.; Stahl, S. S. J. Am. Chem. Soc. 2010, 132, 12068-12073. (d) Casita, A.; King, A. E.; Prella, T.; Costas, M.; Stahl, S. S.; Ribas, X. J. Chem. Sci. 2010, 1, 326-330.

5. Vinyl boronic acids: Lam, P. Y. S.; Vincent, G.; Bonne, D.; Clark, C. G. Tetrahedron Lett. 2003, 44, 4927-4931.

6. Intramolecular: Decicco, C. P.; Song, Y.; Evans, D.A. Org. Lett. 2001, 3, 1029-1032.

7. Solid phase: (a) Combs, A. P.; Saubern, S.; Rafalski, M.; Lam, P. Y. S. Tetrahedron Lett. 1999, 40, 1623-1626. (b) Combs, A. P.; Tadesse, S.; Rafalski, M.; Haque, T. S.; Lam, P. Y. S. J. Comb. Chem. 2002, 4, 179-182.

8. Boronates/borates: (a) Chan, D. M. T.; Monaco, K. L.; Li, R.; Bonne, D.; Clark, C. G.; Lam, P. Y. S. Tetrahedron Lett. 2003, 44, 3863􀀐3865. (b) Yu, X. Q.; Yamamoto, Y.; Miyuara, N. Chem. Asian J. 2008, 3, 1517-1522.

9. Siloxanes: (a) Lam, P. Y. S.; Deudon, S.; Averill, K. M.; Li, R.; He, M. Y.; DeShong, P.; Clark, C. G. J. Am. Chem. Soc. 2000, 122, 7600-7601. (b) Lam, P. Y. S.; Deudon, S.; Hauptman, E.; Clark, C. G. Tetrahedron Lett. 2001, 42, 2427-2429.

10. Stannanes: Lam, P. Y. S.; Vincent, G.; Bonne, D.; Clark, C. G. Tetrahedron Lett. 2002, 43, 3091-3094.

11. Thiols: (a) Herradura, P. S.; Pendora, K. A.; Guy, R. K. Org. Lett. 2000, 2, 2019-2022. (b) Savarin, C.; Srogl, J.; Liebeskind, L. S. . Org. Lett. 2002, 4, 4309-4312. (c) Xu, H.-J.; Zhao, Y.-Q.; Feng, T.; Feng, Y.-S. J. Org.Chem. 2012, 77, 2878-2884.

12. Sulfinates: (a) Beaulieu, C.; Guay. D.; Wang, C.; Evans, D. A. Tetrahedron Lett. 2004, 45, 3233-3236. (b) Huang, H.; Batey, R. A. Tetrahedron. 2007, 63, 7667-7672. (c) Kar, A.; Sayyed, L.A.; Lo, W.F.; Kaiser, H.M.; Beller, M.; Tse,M. K. Org. Lett. 2007, 9, 3405-3408.

13. Sulfoximines: Moessner, C.; Bolm, C. Org. Lett. 2005, 7, 2667-2669.

14. β-Lactam: Wang, W.; et al. Bio. Med. Chem. Lett. 2008, 18, 1939-1944.

15. Cyclopropyl boronic acid: Tsuritani, T.; Strotman, N. A.; Yamamoto, Y.; Kawasaki, M.; Yasuda, N.; Mase, T. Org. Lett. 2008, 10, 1653-1655.

16. Alcohols: Quach, T. D.; Batey, R. A. Org. Lett. 2003, 5, 1381-1384.

17. Fluorides: (a) Ye, Y.; Sanford, M. S. J. Am. Chem. Soc. 2013, 135, 4648-4651.(b) Fier, P. S.; Luo, J.; Hartwig, J. F. J. Am. Chem. Soc. 2013, 135, 2552-2559.

編譯自:J.J. Li, Name Reactions: A Collection of Detailed Mechanisms and Synthetic Applications, Chan–Lam C–X coupling reaction,page 125-127.

實驗技巧

一、該反應在惰性氣體的保護下反應很難進行。

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