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Supervisor: Yong HuangReporter: Qian WangDate: 2015-10-26

Magical Chiral Spirobiindane Skeletons

Contents1. The origin of spirobiindane skeletons2. The development and application3. Comparison of biaryls and spiranes4. Summary and Outlook5. Acknowledgement2developmentQilin ZhouSBINOLBirmanSpirOPXinzi ChenSpiro[4.4]nonaneKumar19921997199920021. The origin of spirobiindane skeletons34Examples of early developed chiral phopshine ligands

Kagan, H. G. J. Am. Chem. Soc. 1972, 94, 6429.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. Sharpless5chirally catalysedHydrogenation reactionschirally catalysedoxidation reactions6The 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, 9570.Sasai, H. Org. Lett. 1999, 1, 1795.Birman, V. B. Tetrahedron: Asymmetry 1999, 1, 1975.Zhou, Q. L. Angew. Chem., Int. Ed. 2002, 41, 2348. Zhou, Q. L. J. Am. Chem. Soc. 2003, 125, 4404.7

Birman, V. B. Tetrahedron: Asymmetry 1999, 1, 1975.8The attempts of synthesis of chiral spiro diphosphine ligands with a spiro[4.4] nonane skeleton

Jiang, Y. Z. J. Am. Chem. Soc. 1997, 119, 9570.Zhang, X. M. J. Am. Chem. Soc. 1997, 119, 1799.9The 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, 5345.102. The development and application11Chiral Spirobiindane1. As metal ligands2. As organic catalystsMonophosphorous ligandsDiphosphine ligandsPhosphine-nitrogen ligandsAminophosphine ligandsBidentate nitrogen ligandsPhosphine-ene ligands121. As metal ligandsChiral spiro monophosphorous ligands

13Chiral spiro diphosphine ligands

Chiral spiro phosphine-nitrogen ligands

14Chiral spiro aminophosphine ligands

Chiral spiro bidentate nitrogen ligands

15Chiral spiro phosphine-ene ligands

16Catalytic asymmetric hydrogenations reactions

Zhou, Q. L. Angew. Chem., Int. Ed. 2002, 41, 2348.Zhou, Q. L. Angew. Chem., Int. Ed. 2005, 44, 1118.Zhou, Q. L.; Chan, A. S. C. Chem. Commun. 2007, 613.

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Zhou, Q. L. Angew. Chem., Int. Ed. 2012, 51, 8872.

....................................................................................................................Catalytic asymmetric hydrogenations reactions

Zhou, Q. L. Angew. Chem., Int. Ed. 2012, 51, 201. 18Asymmetric carbon-carbon bond forming reactionsZhou, Q. L. J. Am. Chem. Soc. 2008, 130, 14052.

Zhou, Q. L. J. Am. Chem. Soc. 2006, 128, 2780............................................................................................................................19Asymmetric carbon-carbon bond forming reactions

Zhou, Q. L. J. Am. Chem. Soc. 2010, 132, 10955.

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Zhou, Q. L. Org. Lett. 2006, 8, 2567. 20Asymmetric carbon-heteroatom bond forming reactions

Zhou, Q. L. Angew. Chem., Int. Ed. 2014, 53, 2978.

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Zhou, Q. L. Angew. Chem., Int. Ed. 2008, 47, 8496.

21Asymmetric carbon-heteroatom bond forming reactions

97% yield, 89% eeCbz = benzyloxycarbonyl

Zhou, Q. L. Angew. Chem., Int. Ed. 2011, 50, 11483-11486.22Asymmetric carbon-heteroatom bond forming reactionsZhou, Q. L. Angew. Chem., Int. Ed. 2011, 50, 11483-11486.

23Catalytic cyclization reactions

Toste, F. D. J. Am. Chem. Soc. 2011, 133, 5500.

Fu, G. C. Angew. Chem., Int. Ed. 2013, 52, 2525.

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24Catalytic cyclization reactions

Zhou, Q. L. Angew. Chem., Int. Ed. 2007, 46, 1275.

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Shu, W.; Yu, Q.; Ma, S. Adv. Synth. Catal. 2009, 351, 2807.

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Hoffman, T. J.; Carreira, E. M. Angew. Chem., Int. Ed. 2011, 50, 10670.Catalytic cyclization reactions262. As organic catalystsEnantioselective Friedel-Crafts Reaction of Indoles with Imines

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....................................Wang, Y. G. et al. J. Org. Chem. 2010, 75, 8677-8680.27Kinetic Resolution of Homoaldols via Catalytic Asymmetric Transacetalization

..........................................................................................................List, B. et al. J. Am. Chem. Soc. 2010, 132, 17370-17373.28The Catalytic Asymmetric Fischer IndolizationList, B. et al. J. Am. Chem. Soc. 2011, 133, 18534-18537.

29The reactions of indoles with aldimines and ,-unsaturated--ketoesters

Hu, Q. S. et al. J. Org. Chem. 2011, 76, 4125-4131.

Hu, Q. S. et al. Eur. J. Org. Chem. 2012, 1115-1118.The reactions of Asymmetric Allylboration of Aldehydes with Pinacol Allylboronates30Highly Enantioselective Pictet-Spengler Reaction

Wang, Y. G. et al. Chem. Eur. J. 2012, 18, 3148-3152.31Highly Enantioselective Biginelli Reaction

Wang, Y. G. et al. Org. Biomol. Chem. 2012, 10, 4467-4470.32Highly Enantioselective Hydrophosphonylation of Imines Reaction

..................................................................................................Lin, X. F. et al. RSC Adv., 2013, 3, 11895-11901.33Highly Enantioselective Three-component Povarov Reaction

Lin, X. F. et al. RSC Adv., 2013, 3, 573-578.343. A comparison of biaryls and spiranes skeletonsMore rigid, a larger dihedral angle.Containing a quaternary center.Smaller molecular weight.More activity and enantioselectivity.

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......................................................................................................Zhou, Q. L. et al. Angew. Chem. Int. Ed. 2002, 41, No. 13.The Rh-P-N angle: 43.6The P-Rh-P angle: 95.6The Rh-P bond lengths: 2.286 Structure of [Rh(cod){(S)-1}]+364. Summary and OutlookAsymmetric hydrogen-ationsasymmetricC-C bondasymmetricC-X bond

chiral spiro skeletonbioactive chiral compounds, chiral natural products and chiral drugs.Developing new chiral spiro ligands and catalysts with high activity and high enantioselectivity.37Prof. Zhous Research Group1051352002-20053/192006-201021/442011-201521/4238As metal ligandsAs organic catalysys

39Prof. HuangMr. ChenAll members hereThanks for your attention!5. Acknowledgement40

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44Prof. Qi-Lin Zhous 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): 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);