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不对称催化的烯烃卤化反应

不对称催化的烯烃卤化反应. 陶忠林 2012/11/24. 1. Introduction 2. Chiral Lewis Base Catalysis 3. Chiral Ion Pairing Catalysis 4. Hydrogen Bonding 5. Lewis Acid Catalysis 6. Conclusion. 1. Introduction. olefin-to-olefin transfer. Catalysis model.

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不对称催化的烯烃卤化反应

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  1. 不对称催化的烯烃卤化反应 陶忠林 2012/11/24

  2. 1. Introduction 2. Chiral Lewis Base Catalysis 3. Chiral Ion Pairing Catalysis 4. Hydrogen Bonding 5. Lewis Acid Catalysis 6. Conclusion

  3. 1. Introduction olefin-to-olefin transfer

  4. Catalysis model Scott E. Denmark,Angew. Chem. Int. Ed. 2012, 51, 10938 – 10953

  5. 2. Chiral Lewis Base Catalysis K. Ishihara, Nature2007, 445, 900 – 903.

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  8. 3. Chiral Ion Pairing Catalysis L. X. Gao, J. Org. Chem. 2004, 69, 2874-2876 R. Frçhlich, Org. Lett. 2011, 13, 860–863.

  9. Y. Shi, Org.Lett. 2011, 13, 6350 – 6353. S. E. Denmark,Org. Lett.2012, 14, 256 – 259.

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  12. 4.Hydrogen Bonding B. Borhan, J. Am. Chem. Soc. 2010, 132, 3298–3300

  13. B. Borhan, J. Am. Chem. Soc. 2010, 132, 3298–3300

  14. 将cat与NBS在溶剂中搅拌20min,再加入反应物： 收率不变，85%ee降为54%； 将cat与NBS在溶剂中搅拌4h,再加入反应物： 收率不变，85%ee降为26%. R1=R3=H,R2=Cl时，DABCO或者BnNHC(O)NHTs单独加，NR。 W. Tang,J. Am. Chem. Soc. 2010, 132, 3664-3665.

  15. Y-Y Yeung J. Am. Chem. Soc.2010, 132, 15474–15476

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  22. 5. Lewis Acid Catalysis T. Taguchi,Tetrahedron Let, 1995, 36, 9333-9336 T. Taguchi, J. Org. Chem. 1997, 62, 7384-7389 S. H. Kang J. Am. Chem. Soc. 2003,125, 15748 – 15749

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  25. 多数的反应都是分子内的反应，而分子间的反应则较少。可能的原因是分子内的反应可以被亲核试剂较快的捕获，从而抑制烯烃到烯烃的转移。多数的反应都是分子内的反应，而分子间的反应则较少。可能的原因是分子内的反应可以被亲核试剂较快的捕获，从而抑制烯烃到烯烃的转移。 • 对反应机理的理解便于我们对反应和催化体系的设计。而这类反应的机理尚不是很清楚，尤其是很多体系需要一些添加剂，增加了体系的复杂性。 • 在近3年，这类反应得到较快的发展，但是同时尚没有较为有效地催化体系。催化剂对底物的适用范围较窄。

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