联萘基单齿磷配体不对称氢化研究进展课件

1、联萘基单齿磷配体不对称氢化研究进展学生：王培远导师：杨启华 研究员Seminar II内容简介背景介绍联萘基单齿磷配体的合成与发展联萘基单齿磷配体在烯烃不对称氢化中的应用前景展望手性工业的税收总额增长趋势及预测(Unit: billion $)生物分子具有手性特征，对生物体系有活性的药物往往是单一手性对映体化合物。手性合成是目前有机化学和催化化学的前沿研究方向。 -Chem. & Eng. News, 2004, Vol 82, No. 24, June 14, 472001年诺贝尔化学奖不对称合成K. Barry SharplessRyoji Noyori野依良治（日本）手性催化氢化反应 巴

2、里夏普雷斯（美国）手性催化氧化反应 William S. Knowles威廉诺尔斯 (美国)手性催化氢化反应 不对称氢化中常用的双磷配体人们普遍认为手性的双齿配体与金属螯和，降低了金属与磷之间化学键的旋转自由度，在一定程度上增加了催化剂的刚性，从而在手性反应中更加利于形成较高的反应活性和ee值Chem. Soc. Rev., 2008, 37, 839MonoPhos 合成及演变P(NMe2)3toluene12h, refluxA 28-year-old synthesis of micelle-templated mesoporous silicaA procedure for the p

3、reparation of low-density silica described in a patent filed in 1969 V. Chiola, J.E. Ritsko, C.D. Vanderpool, US Patent 3 556 725, 1971 leads to the formation of solids having all the properties of MCM-41, the ordered mesoporous silica disclosed in 1991 J.S. Beck, C.T.-W. Chu, I.D. Johnson, C.T. Kre

4、sge, M.E. Leonowicz, W.J. Roth, J.W. Vartuli, WO Patent 91/11390, 1991.Tetrahedron: Asymmetry, 1994, 5, 699Microporous Mater. 1997, 10, 283手性配体的合成J. Am. Chem. Soc. 2000, 122, 11539金属/配体、底物、压力Adv. Synth. Catal. 2003, 345,308L(S)-a(S)-b(S)-c(S)-d(S)-e(S)-fAngew. Chem., Int. Ed. 2000, 39, 3889Why Are B

5、INOL-Based Monophosphites Such Efficient Ligands in Rh-Catalyzed Asymmetric Olefin HydrogenationInfluence of pressure on the hydrogenation of using Rh(L)2-(cod)BF4 as catalyst.OCH2C6H5oxidative addition of H2 is the rate-determining stepJ. Am. Chem. Soc. 2005, 127, 10305Rh/ligand ratio of 1:2 is opt

6、imalInfluence of Rh/L on the hydrogenation of using Rh(L)2-(cod)BF4 as catalyst.Why Are BINOL-Based Monophosphites Such Efficient Ligands in Rh-Catalyzed Asymmetric Olefin HydrogenationJ. Am. Chem. Soc. 2005, 127, 10305Why Are BINOL-Based Monophosphites Such Efficient Ligands in Rh-Catalyzed Asymmet

7、ric Olefin HydrogenationRu/(L)2遵从锁钥匙理论“I think we are far from having a general understanding of asymmetric homogeneous hydrogenation after 30 years of research.” (Thomas Riermeier )J. Am. Chem. Soc. 2005, 127, 10305Zheng Z, et al., Org. Lett. 2003, 5, 4137Zheng Z, et al., J. Org. Chem. 2004, 69, 23

8、55Zheng Z, et al., Tetrahedron: Asymmetry 2004, 15, 2011衣康酸二甲酯-芳基烯酰胺-脱氢氨基酸酯Ee=89-99%“Nothing comes without a hidden cost or flip side.” “Asymmetric catalysis is a great boon but carries with it the problem of having to deal with residual metals.”Chem. & Eng. News, 2005, Vol 83, No. 36, September 5 ,

9、 5固载化：聚合物Tetrahedron Lett. 2006, 47, 4263Tetrahedron Lett., 2006, 47, 426392.3-96.4%ee83.4-96.5%ee85.1-96.5%ee固载化：AlTUD-1Chem. Commun., 2004,24,2830 固载化:介孔材料J. Catal., 2008, 254, 91参考文献1. Chem. & Eng. News, 2004, Vol 82, No. 24, June 14, 47.2. Eberhardt, L. et al. Chem. Soc. Rev., 2008, 37, 839.3. R

10、eetz, M. T. et al. Angew. Chem., Int. Ed., 2000, 39, 3889.4. Feringa, B. L. et al. J. Am. Chem. Soc., 2000, 122, 11539.5. Pringle, P. G. et al. Chem. Commun., 2000, 961.6. Reetz, M. T. et al. Tetrahedron Lett., 2000, 41.7. Feringa, B. L. et al. Tetrahedron: Asymmetry, 1994, 5, 699.8. Vries, J. G. de

11、, et al. Adv. Synth. Catal., 2003, 345, 308.9. Reetz, M. T. et al. J. Am. Chem. Soc., 2005, 127, 10305.10. Zheng Z, et al., Org. Lett. ,2003, 5, 4137.11. Zheng Z, et al., J. Org. Chem. ,2004, 69, 2355.12. Zheng Z, et al., Tetrahedron: Asymmetry, 2004, 15, 2011.13. Tetrahedron Lett., 2006, 47, 4263.14. Chem. Commun., 2004,24,2830.15. Halligudi, S. B. et al. J. Catal., 2008, 254, 91.16. Feringa, B. L. Acc. Chem. Res., 2000, 33, 346.17. Chem. & Eng. Ne