树状分子催化剂

       基于酶催化原理，以树状分子为载体，利用树状大分子独特的物理化学性质及其精确可控的分子三维立体结构，通过分子设计在树状分子的表面或核心引入（手性）催化活性中心，构建具有“协同”或“孤立”效应的（手性）催化剂新体系是催化研究领域的前沿和热点之一。我们选择性能优异的小分子配体为研究对象，发展了系列新型树状分子催化剂以及催化剂分离回收新方法。研究表明：树状分子载体不仅方便催化剂的分离与回收，而且更重要的是可以调控催化剂的催化活性和立体选择性，提高催化剂的稳定性能，为负载均相催化剂的分子设计开辟了新的途径。

Figure. Dendritic Ligands/Catalysts and Their Applications in Catalysis 

 

40. Yan-Mei He, Yu Feng, Qing-Hua Fan*, "Asymmetric hydrogenation in the core of dendrimers", Acc. Chem. Res. 2014, 47, 2894-2906.

39. Baode Ma, Tingting Miao, Yihua Sun, Yanmei He, Ji Liu, Yu Feng, Hui Chen,* Qing-Hua Fan*, "A new class of tunable dendritic diphosphine ligands: synthesis and applications in the ru-catalyzed asymmetric hydrogenation of functionalized ketones", Chem. Eur. J. 2014,20, 9969-9978. 

 

38. Ji Liu, Baode Ma, Yu Feng, Yanmei He,* and Qing-Hua Fan,* "Dendritic [Rucl₂(BINAP)(DPEN)] Catalysts with 'Sandwich' Multi-Layer Structure for Asymmetric Hydrogenation of Simple Aryl Ketones", Inorgan. Chim. Acta 2014, 409, 106-111.

37. Baode Ma, Guojun Deng, Ji Liu, Yanmei He and Qing-Hua Fan,* "Synthesis of Dendritic BINAP Ligands and Their Applications in the Asymmetric Hydrogenation: Exploring the Relationship between Catalyst Structure and Catalytic Performance", Acta Chim. Sinica 2013, 71, 528-534.

36. Baode Ma, Ziyuan Ding, Ji Liu, Yanmei He and Qing-Hua Fan,* "Highly Enantioselective Hydrogenation of 2,4-Diaryl-1,5-Benzodiazepines Catalyzed by Dendritic Phosphinooxazoline Iridium Complexes", Chem. Asian J. 2013, 8, 1101-1104.

35. Ji Liu, Yu Feng, Baode Ma, Yan-Mei He and Qing-Hua Fan,* "Design and Synthesis of Janus-Type Chiral Dendritic Diphosphanes and Their Applications in Asymmetric Hydrogenation", Eur. J. Org. Chem. 2012, 6737-6744.

34. Liwen Zhao, Ji Liu, Yu Feng, Yanmei He and Qing-Hua Fan,* "Facile Synthesis of Chiral Diphosphine-Containing Multiple Dendrimeric Catalysts for Enantioselective Hydrogenation", Chin. J. Chem. 2012, 30, 2009-2015.

33. Ji Liu, Yu Feng, Yanmei He, Nianfa Yang* and Qing-Hua Fan,* "Janus Dendritic Phosphines: Synthesis and Application in Suzuki Coupling Reactions", New J. Chem. 2012, 36, 380-385.

 32. Baode Ma and Qinghua Fan,* "Progress on Chiral Dendrimeric Phosphorous Ligands in Asymmetric Catalytic Hydrogenations", Sci. Sinica Chim. 2010, 40, 827-836.

31. Bing Yi,* Hua-Ping He and Qing-Hua Fan, "Synthesis and Application of Peripherally Alkyl-Functionalized Dendritic Pyrphos Ligands: Homogeneous-Supported Catalysts for Enantioselective Hydrogenation", J. Mol. Catal. A: Chem. 2010, 315, 82-85.

30. Feng Zhang and Qing-Hua Fan,* "Synthesis and Application of Bulky Phosphoramidites: Highly Effective Monophosphorus Ligands for Asymmetric Hydrosilylation of Styrenes", Org. Biomol. Chem. 2009, 7, 4470-4474.

 29. Yong Li, Yan-Mei He, Zhi-Wei Li, Feng Zhang and Qing-Hua Fan,* "Supramolecular Chiral Dendritic Monophosphites Assembled by Hydrogen Bonding and Their Use in The Rh-Catalyzed Asymmetric Hydrogenation", Org. Biomol. Chem. 2009, 7, 1890-1895.

 28. Feng Zhang, Yong Li, Zhi-Wei Li, Yan-Mei He, Shou-Fei Zhu, Qing-Hua Fan* and Qi-Lin Zhou,* "Modular Chiral Dendritic Monodentate Phosphoramidite Ligands for Rh(II)-Catalyzed Asymmetric Hydrogenation: Unprecedented Enhancement of Enantioselectivity", Chem. Commun. 2008, 6048-6050.

27. Lei Wu, Zhi-Wei Li, Feng Zhang, Yan-Mei He and Qing-Hua Fan,* "Air-Stable and Highly Active Dendritic Phosphine Oxide-Stabilized Palladium Nanoparticles: Preparation, Characterization and Applications in the Carbon-Carbon Bond Formation and Hydrogenation Reactions", Adv. Synth. Catal. 2008, 350, 846-862. <Highlight by Synfacts 2008, 8, 882.>

26. Yu Feng, Yan-Mei He, Li-Wen Zhao, Yi-Yong Huang and Qing-Hua Fan,* "A Liquid-Phase Approach to Functionalized Janus Dendrimers: Novel Soluble Supports for Organic Synthesis", Org. Lett. 2007, 9, 2261-2264.

 

25. Zhi-Jian Wang, Guo-Jun Deng, Yong Li, Yan-Mei He, Wei-Jun Tang and Qing-Hua Fan,* "Enantioselective Hydrogenation of Quinolines Catalyzed by Ir(BINAP)-Cored Dendrimers: Dramatic Enhancement of Catalytic Activity" Org. Lett. 2007, 9, 1243-1246.

24. Liwen Zhao, Qing-Hua Fan,* Haifeng Zhou, Yanmei He, Lianquan Gu* and Albert S. C. Chan,* "Study of Dendrimers as Supports for Organic Synthesis", Prog. Chem. 2006, 18, 317-330.

23. Wei-Jun Tang, Yi-Yong Huang, Yan-Mei He and Qing-Hua Fan,* "Dendritic MonoPhos: Synthesis and Application in Rh-Catalyzed Asymmetric Hydrogenation", Tetrahedron: Asymmetry 2006, 17, 536-543.

22. Guo-Jun Deng, Guo-Rui Li, Ling-Yun Zhu, Hai-Feng Zhou,Yan-Mei He, Qing-Hua Fan* and Zhi-Gang Shuai,* "Dendritic BIPHEP: Synthesis and Application in Asymmetric Hydrogenation of β-Ketoesters", J. Mol. Catal. A: Chem. 2006, 244, 118-123.

21. Lei Wu, Bao-Lin Li, Yi-Yong Huang, Hai-Feng Zhou, Yan-Mei He and Qing-Hua Fan,* "Phosphine Dendrimer-Stabilized Palladium Nanoparticles, a Highly Active and Recyclable Catalyst for the Suzuki-Miyaura Reaction and Hydrogenation", Org. Lett. 2006, 8, 3605-3608. <Highlight by Synfacts 2006, 11, 1185.>

20. Yi-Yong Huang, Yan-Mei He, Hai-Feng Zhou, Lei Wu, Bao-Lin Li and Qing-Hua Fan,* "Thermomorphic System with Non-Fluorous Phase-Tagged Ru(BINAP) Catalyst: Facile Liquid/Solid Catalyst Separation and Application in Asymmetric Hydrogenation", J. Org. Chem. 2006, 71, 2874-2877.

19. Yi-Yong Huang, Hai-Liang Zhang, Guo-Jun Deng, Wei-Jun Tang, Xia-Yu Wang,* Yan-Mei He and Qing-Hua Fan,* "Synthesis of Triphenylphosphine-Functionalized Dendrimers and Application to Olefin Hydroformylation", J. Mol. Catal. A: Chem. 2005, 227, 91-96.

18. Nian-Fa Yang,* Hang Gong, Wei-Jun Tang, Qing-Hua Fan, Chang-Qun Cai and Li-Wen Yang, "Phase Selectively Soluble Dendritic Derivative of 4-(N,N-Dimethylamino)Pyridine: An Easily Recyclable Catalyst for Baylis-Hillman Reactions", J. Mol. Catal. A: Chem. 2005, 233, 55-59.

17. Hang Gong, Nian-Fa Yang,* Wei-Jun Tang, Qing-Hua Fan and Li-Wen Yang, "Phase Selectively Soluble Dendritic Derivative of 4-(Dimethylamino)Pyridine: An Easily Recyclable Catalyst for Baylis-Hillman Reactions", Chinese Chem. Lett. 2005, 16, 1017-1020.

16. Weiguo Liu, Xin Cui, Linfeng Cun, Jun Wu, Jin Zhu, Jingen Deng* and Qing-Hua Fan, "Novel Dendritic Ligands of Chiral 1,2-Diamine and Their Application in Asymmetric Hydrogenation of Simple Aryl Ketones", Synlett 2005, 1591-1595.

15. Dai-Hua Tang, Xiao-Min Chen and Qing-Hua Fan,* "A Convenient Route to Dendritic Binaphthyl-Containing Chiral Crown Ethers", J. Chem. Res. 2004, 702-703.

14. Wei-Jun Tang, Nian-Fa Yang,* Bing Yi, Guo-Jun Deng, Yi-Yong Huang and Qing-Hua Fan,* "Phase Selectively Soluble Dendrimer-Bound Osmium Complex: A Highly Effective and Easily Recyclable Catalyst for Olefin Dihydroxylation", Chem. Commun. 2004, 1378-1379.

13. Guo-Jun Deng, Bing Yi, Yi-Yong Huang, Wei-Jun Tang, Yan-Mei He and Qing-Hua Fan,* "Dendronized Poly(Ru-BINAP) Complexes: Highly Effective and Easily Recyclable Catalysts for Asymmetric Hydrogenation", Adv. Synth. Catal. 2004, 346, 1440-1444.

12. Bing Yi, Qing-Hua Fan,* Guo-Jun Deng, Yue-Ming Li, Li-Qin Qiu and Albert S. C. Chan,* "Novel Chiral Dendritic Diphosphine Ligands for Rh(I)-Catalyzed Asymmetric Hydrogenation: Remarkable Structural Effects on Catalytic Properties", Org. Lett. 2004, 6, 1361-1364.

11. Guo-Hua Liu and Qing-Hua Fan,* Xi-Qiang Yang and Xiao-Min Chen, "Chiral BINOL-Centered Dendrimers for The Enantioselective Lewis Acid Catalyzed Diethylzinc Addition to Aldehydes", Arkivoc 2003, 123-132.

10. Dai-Hua Tang and Qing-Hua Fan,* "Convergent Synthesis of AB₂-AB₃ Hybrid-Type of Amphiphilic Oligoethyleneoxy-Modified Poly(Benzyl Ether) Dendrons", J. Chem. Res. 2003, 698-699.

9. Qing-Hua Fan, Xi-Qiang Yang, Guo-Hua Liu, Xiao-Min Chen and Albert S. C. Chan, "Synthesis of New Dendritic Chiral BINOL Ligands and Their Applications in Enantioselective Lewis Acid Catalyzed Addition of Diethylzinc to Aldehydes", Chem. J. Chinese. Univ. 2003, 274-277.

8. Guo-Jun Deng, Qing-Hua Fan,* Xiao-Min Chen and Guo-Hua Liu, "Dendritic BINAP Based System for Asymmetric Hydrogenation of Simple Aryl Ketones", J. Mol. Catal. A: Chem. 2003, 193, 21-25.

7. Bai-Yuan Yang, Xiao-Min Chen,* Guo-Jun Deng, Yi-Li Zhang and Qing-Hua Fan,* "Chiral Dendritic Bis(Oxazoline) Copper(II) Complexes as Lewis Acid Catalysts for Enantioselective Aldol Reactions in Aqueous Media", Tetrahedron Lett. 2003, 44, 3535-3538.

6. Guo-Hua Liu, Wei-Jun Tang and Qing-Hua Fan,* "Dendritic BINOL Ligands for Asymmetric Aatalysis: Effect of the Linking Positions and Generations of the Dendritic Wedges on Catalyst Properties", Tetrahedron 2003, 59, 8603-8611.

5. Qing-Hua Fan,* Rui Zhang, Guo-Jun Deng and Xiao-Min Chen, "The Synthesis of Amphiphilic Chiral Dendritic 1,1'-Bi-2-Naphthol Derivatives and Their Application as Amphiphiles in Aqueous Asymmetric Hydrogenation", J. Chem. Res. 2002, 318-320.

4. Guo-Jun Deng, Qing-Hua Fan,* Xiao-Min Chen, Dong-Shen Liu and Albert S. C. Chan, "A Novel System Consisting of Dendritic Ru-BINAP for Asymmetric Hydrogenation and Catalyst Recycling", Chem. Commun. 2002, 1570-1571.

3. Qing-Hua Fan, Yue-Ming Li* and Albert S. C. Chan,* "Recoverable Catalysts for Asymmetric Organic Synthesis", Chem. Rev. 2002, 102, 3385-3466.

2. Qing-Hua Fan,* Guo-Hua Liu, Xiao-Min Chen, Guo-Jun Deng and Albert S. C. Chan,* "The Synthesis of Dendritic BINOL Ligands and Their Applications in Enantioselective Lewis Acid Catalyzed Addition of Diethylzinc to Aldehydes", Tetrahedron: Asymmetry 2001, 12, 1559-1565.

1. Qing-Hua Fan,* Yong-Ming Chen, Xiao-Min Chen, Da-Zhi Jiang, Fu Xi and Albert S. C. Chan,* "Highly Effective and Recyclable Dendritic BINAP Ligands for Asymmetric Hydrogenation", Chem. Commun. 2000, 789-790.