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单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,*,单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,*,不对称催化的烯烃卤化反应,2012/11/24,1,1. Introduction,2. Chiral Lewis Base Catalysis,3. Chiral Ion Pairing Catalysis,4. Hydrogen Bonding,5. Lewis Acid Catalysis,6. Conclusion,2,1.,Introduction,olefin-to-olefin transfer,3,Catalysis model,Scott E. Denmark,Angew. Chem. Int. Ed,.,2012,51, 10938,10953,4,2. Chiral Lewis Base Catalysis,K. Ishihara,Nature,2007,445, 900 903.,5,N. Shibata,Angew. Chem.Int. Ed,.,2008,47, 4157 - 4161.,V,.,Gouverneur,Angew. Chem. Int. Ed,.,2011,50, 8105 8109,6,E,.,N. Jacobsen,Angew. Chem. Int. Ed.,2010,49, 7332 7335,7,3. Chiral Ion Pairing Catalysis,R. Frhlich,Org. Lett,.,2011,13,860863.,L. X. Gao,J. Org. Chem.,2004,69, 2874-2876,8,Y. Shi,Org.Lett,.,2011,13, 6350 6353.,S. E. Denmark,Org. Lett.,2012,14,256 259.,9,F. D. Toste,Science,，,2011,334, 1681 1684,10,Z,. Tang,Tetrahedron Asymmetry,.,2012,23,245251,J,.,N. Johnston,J. Am. Chem. Soc,.,2012,134, 60686071,11,4.Hydrogen Bonding,B,.,Borhan,J. Am. Chem. Soc,.,2010,132, 32983300,12,B,.,Borhan,J. Am. Chem. Soc,.,2010,132, 32983300,13,W. Tang,J. Am. Chem. Soc,.,2010,132, 3664-3665,.,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,。,14,Y-Y Yeung,J. Am. Chem. Soc.,2010,132, 1547415476,15,Y-Y Yeung,Angew. Chem. Int. Ed,.,2012,51,7771 7775,Y-Y Yeung,J. Am. Chem. Soc,.,2011,133,91649167,16,Y-Y Yeung,Chem. Commun.,2012,48, 57935795,Y-Y Yeung,Org. Biomol. Chem,.,2012,10,38083811,17,K. C. Nicolaou,J. Am. Chem. Soc,.,2011,133, 81348137,H. Fujioka,Angew. Chem. Int. Ed.,2010,49, 9174 9177,H. Fujioka,Chem. Eur. J.,2012,18,8448 8453,18,B. Borhan,Angew. Chem. Int. Ed,.,2011,50,2593 2596,S. J. Miller,Science,2010,328, 1251 1255.,19,Y,.,Q,.,Tu,J. Am. Chem. Soc.,2011,133, 88188821,Y,.,Q,.,Tu,Chem. Sci,.,2011,2, 1839 1841,U. Hennecke, Synlett 2011, 2043 2047.,20,S. F. Martin,J. Am. Chem. Soc,.,2012,134, 1112811131,21,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 15749,5. Lewis Acid Catalysis,22,P. M. Henry,Org. Lett,.,2003,5, 439 441,Xiaoming Feng,Angew. Chem. Int. Ed,.,2010,49, 6160 6164,Chem. Eur. J.,2011,17,14916 14921,23,Xiaoming Feng,J. Am. Chem. Soc,.,2011,133,56365639,24,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。,25,
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