Supervisor: Yong Huang Reporter: Qian Wang Date: Magical Chiral Spirobiindane Skeletons

Contents 1. The origin of spirobiindane skeletons 2. The development and application 3. Comparison of biaryls and spiranes 4. Summary and Outlook 5. Acknowledgement 2

development Qilin Zhou SBINOL Birman SpirOP Xinzi Chen Spiro[4.4]nonane Kumar The origin of spirobiindane skeletons 3

4 Examples of early developed chiral phopshine ligands Kagan, H. G. J. Am. Chem. Soc. 1972, 94, Knowles, W. S. Chem. Soc., Chem. Commun. 1972, 10. Knowles. W. S. Acc. Chem. Res. 1983, 16, 106. Noyori, R. J. Am. Chem. Soc. 1980, 102, 7932.

The Nobel Prize in Chemistry 2001 W. S. KnowlesR. NoyoriK. B. Sharpless 5 “chirally catalysed Hydrogenation reactions” “chirally catalysed oxidation reactions”

6 The early attention and development of chiral spiro compounds and ligands Kumar, A. Chem. Commun. 1992, 493. Jiang, Y. Z. J. Am. Chem. Soc. 1997, 119, Sasai, H. Org. Lett. 1999, 1, Birman, V. B. Tetrahedron: Asymmetry 1999, 1, Zhou, Q. L. Angew. Chem., Int. Ed. 2002, 41, Zhou, Q. L. J. Am. Chem. Soc. 2003, 125, 4404.

7 Birman, V. B. Tetrahedron: Asymmetry 1999, 1, 1975.

8 The attempts of synthesis of chiral spiro diphosphine ligands with a spiro[4.4] nonane skeleton Jiang, Y. Z. J. Am. Chem. Soc. 1997, 119, Zhang, X. M. J. Am. Chem. Soc. 1997, 119, 1799.

9 The spirobiindane and spiro[4.4]nonadiene skeletons and their chiral spiro ligands Zhou, Q. L. Chem. Commun. 2002, 480. Ding, K. L. Angew. Chem., Int. Ed. 2009, 48, 5345.

10 2. The development and application

11 Chiral Spirobiindane 1. As metal ligands 2. As organic catalysts  Monophosphorous ligands  Diphosphine ligands  Phosphine-nitrogen ligands  Aminophosphine ligands  Bidentate nitrogen ligands  Phosphine-ene ligands

12 1. As metal ligands  Chiral spiro monophosphorous ligands

13  Chiral spiro diphosphine ligands  Chiral spiro phosphine-nitrogen ligands

14  Chiral spiro aminophosphine ligands  Chiral spiro bidentate nitrogen ligands

15  Chiral spiro phosphine-ene ligands

16  Catalytic asymmetric hydrogenations reactions Zhou, Q. L. Angew. Chem., Int. Ed. 2002, 41, Zhou, Q. L. Angew. Chem., Int. Ed. 2005, 44, Zhou, Q. L.; Chan, A. S. C. Chem. Commun. 2007,

17 Zhou, Q. L. Angew. Chem., Int. Ed. 2012, 51,  Catalytic asymmetric hydrogenations reactions Zhou, Q. L. Angew. Chem., Int. Ed. 2012, 51, 201.

18  Asymmetric carbon-carbon bond forming reactions Zhou, Q. L. J. Am. Chem. Soc. 2008, 130, Zhou, Q. L. J. Am. Chem. Soc. 2006, 128,

19  Asymmetric carbon-carbon bond forming reactions Zhou, Q. L. J. Am. Chem. Soc. 2010, 132, Zhou, Q. L. Org. Lett. 2006, 8, 2567.

20  Asymmetric carbon-heteroatom bond forming reactions Zhou, Q. L. Angew. Chem., Int. Ed. 2014, 53, Zhou, Q. L. Angew. Chem., Int. Ed. 2008, 47, 8496.

21  Asymmetric carbon-heteroatom bond forming reactions 97% yield, 89% ee Cbz = benzyloxycarbonyl Zhou, Q. L. Angew. Chem., Int. Ed. 2011, 50,

22  Asymmetric carbon-heteroatom bond forming reactions Zhou, Q. L. Angew. Chem., Int. Ed. 2011, 50,

23  Catalytic cyclization reactions Toste, F. D. J. Am. Chem. Soc. 2011, 133, Fu, G. C. Angew. Chem., Int. Ed. 2013, 52,

24  Catalytic cyclization reactions Zhou, Q. L. Angew. Chem., Int. Ed. 2007, 46, Shu, W.; Yu, Q.; Ma, S. Adv. Synth. Catal. 2009, 351, 2807.

25 Hoffman, T. J.; Carreira, E. M. Angew. Chem., Int. Ed. 2011, 50,  Catalytic cyclization reactions

26 2. As organic catalysts Enantioselective Friedel-Crafts Reaction of Indoles with Imines Wang, Y. G. et al. J. Org. Chem. 2010, 75,

27 Kinetic Resolution of Homoaldols via Catalytic Asymmetric Transacetalization List, B. et al. J. Am. Chem. Soc. 2010, 132,

28 The Catalytic Asymmetric Fischer Indolization List, B. et al. J. Am. Chem. Soc. 2011, 133,

29 The reactions of indoles with aldimines and β,γ-unsaturated-α-ketoesters Hu, Q. S. et al. J. Org. Chem. 2011, 76, Hu, Q. S. et al. Eur. J. Org. Chem. 2012, The reactions of Asymmetric Allylboration of Aldehydes with Pinacol Allylboronates

30 Highly Enantioselective Pictet-Spengler Reaction Wang, Y. G. et al. Chem. Eur. J. 2012, 18,

31 Highly Enantioselective Biginelli Reaction Wang, Y. G. et al. Org. Biomol. Chem. 2012, 10,

32 Highly Enantioselective Hydrophosphonylation of Imines Reaction Lin, X. F. et al. RSC Adv., 2013, 3,

33 Highly Enantioselective Three-component Povarov Reaction Lin, X. F. et al. RSC Adv., 2013, 3,

34 3. A comparison of biaryls and spiranes skeletons More rigid, a larger dihedral angle. Containing a quaternary center. Smaller molecular weight. More activity and enantioselectivity.

Zhou, Q. L. et al. Angew. Chem. Int. Ed. 2002, 41, No. 13. The Rh-P-N angle: 43.6° The P-Rh-P angle: 95.6° The Rh-P bond lengths: Å Structure of [Rh(cod){(S)-1}] +

36 4. Summary and Outlook Asymmetric hydrogen- ations asymmetric C-C bond asymmetric C-X bond chiral spiro skeleton bioactive chiral compounds, chiral natural products and chiral drugs. Developing new chiral spiro ligands and catalysts with high activity and high enantioselectivity.

37 Prof. Zhou’s Research Group / / / / / /42

38 As metal ligands As organic catalysys

39  Prof. Huang  Mr. Chen  All members here Thanks for your attention! 5. Acknowledgement

40

41

42

43

44 Prof. Qi-Lin Zhou’s Research Group (105/135) 2002(3): Tetrahedron(1); Angew. Chem.(1); Chem. Commun.(1) 2003(4): Tetrahedron(2); J. Org. Chem.(1); J. Am. Chem. Soc.(1) 2004(5): Tetrahedron(1); J. Org. Chem.(2); Org. Lett.(1); Adv. Synth. Catal.(1) 2005(7): Tetrahedron(1); J. Org. Chem.(2); Org. Lett.(1); Adv. Synth. Catal.(1) Angew. Chem.(1); Pure. Appl. Chem.(1) 2006(13): 高等学校化学学报； Science in China: Series B chemistry(1); Tetrahedron(3); J. Org. Chem.(1); Org. Lett.(2); Adv. Synth. Catal.(1); J. Am. Chem. Soc.(3); Synlett.(1) 2007(7): Angew. Chem.(2); Adv. Synth. Catal.(1); J. Am. Chem. Soc.(4) 2008(7): Chem. Asian. J.(1); Angew. Chem.(3); J. Am. Chem. Soc.(2); Acc. Chem. Res.(1) 2009(8): J. Am. Chem. Soc.(2); Chem. Commun.(1); Tetrahedron(1); Org. Lett.(1); Adv. Synth. Catal.(2); Front. Chem. China(1) 2010(9): J. Am. Chem. Soc.(4); Tetrahedron(1); Nature Chemistry(1); Science China chemistry(1); Chinese J. Chem.(1); Adv. Synth. Catal.(1) 2011(7): Chem. Sci.(1); Angew. Chem.(2); Org. Lett.(1); Adv. Synth. Catal.(1); Chem. Asian J(1); Synlett.(1) 2012(10): Angew. Chem.(3); J. Am. Chem. Soc.(1); Adv. Synth. Catal.(1); Tetrahedron(1);