Jacobsen–Katsuki环氧化反应

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利用Mn(III)salen催化剂催化下氧化(Z)烯烃不对称合成环氧化物的反应。


反应机理

首先氧化Mn(III)-salen络合物得到Mn(v)活性中间体,反应的对映选择性可以由Jacobsen提出的烯烃从催化剂的顶端进行反应 或Katsuki提出的从侧上方进行反应来解释。


有三种可能的反应机理:


反应实例



参考文献

1. (a) Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N. J. Am. Chem. Soc. 1990,112, 2801–2903. (b) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. TetrahedronLett. 1990, 31, 7345–7348. (c) Irie, R.; Noda, K.; Ito, Y.; Katsuki, T. Tetrahedron Lett. 1991, 32, 1055–1058. (d) Deng, L.; Jacobsen, E. N. J. Org. Chem. 1992,57, 4320–4323. (e) Palucki, M.; McCormick, G. J.; Jacobsen, E. N. Tetrahedron Lett.1995, 36, 5457–5460.

2. Zhang, W.; Jacobsen, E. N. J. Org. Chem. 1991, 56, 2296–2298.

3. Jacobsen, E. N. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH: Weinheim, New York, 1993, Ch. 4.2. (Review).

4. Jacobsen, E. N. In Comprehensive Organometallic Chemistry II, Eds. G. W. Wilkinson,G. W.; Stone, F. G. A.; Abel, E. W.; Hegedus, L. S., Pergamon, New York,1995, vol 12, Chapter 11.1. (Review).

5. Lynch, J. E.; Choi, W.-B.; Churchill, H. R. O.; Volante, R. P.; Reamer, R. A.; Ball, R. G. J. Org. Chem. 1997, 62, 9223–9228.

6. Senananyake, C. H. Aldrichimica Acta 1998, 31, 3–15. (Review).

7. Jacobsen, E. N.; Wu, M. H. In Comprehensive Asymmetric Catalysis, Jacobsen, E. N.; Pfaltz, A.; Yamamoto, H. Eds.; Springer: New York; 1999, Chapter 18.2. (Review).

8. Katsuki, T. In Catalytic Asymmetric Synthesis; 2nd edn.; Ojima, I., Ed.; Wiley-VCH: New York, 2000, 287. (Review).

9. Katsuki, T. Synlett 2003, 281–297. (Review).

10. Palucki, M. Jacobsen–Katsuki epoxidation. In Name Reactions in Heterocyclic Chemistry; Li, J. J., Ed.; Wiley: Hoboken, NJ, 2005, pp 29-43. (Review).

11. Engelhardt, U.; Linker, T. Chem. Commun. 2005, 1152–1154.

12. Fernandez de la Pradilla, R.; Castellanos, A.; Osante, I.; Colomer, I.; Sanchez, M. I. J.Org. Chem. 2009, 74, 170–181.

13. Olson, J. A.; Shea, K. M. Acc. Chem. Res. 2011, 44, 311–321. (Review).


编译自:Name Reactions (A Collection of Detailed Reaction Mechanisms), Jie Jack Li, Jacobsen–Katsuki epoxidation,page 329-330.


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