1. 1 何 龙 西华师范大学化学化工学院 Brønsted Acid-Catalyzed Asymmetric Three- Component 1,3-Dipolar Cycloaddition Reaction 化学应用与污染控制技术重点实验室年会， 2010 ， 12 ， 12

2. 2  The Importance of Pyrrolidine in Natural and Unnatural Biologically Active Products

3. 3  Control of Stereochemistry with Chiral LA-Bonded Dipole. M = Cu, Ag, Zn, Ni, Co; L= chiral diphosphines, N-P ligands Early examples: (a) Longmire, J. M.; Wang, B.; Zhang, X. J. Am. Chem. Soc. 2002, 124, 13400. (b) Gothelf, A. S.; Gothelf, K. V.; Hazell, R. G.; Jorgensen, K. A. Angew. Chem., Int. Ed. 2002, 41, 4236. Reviews: Nájera, C.; Sansano, J. M. Angew. Chem., Int. Ed. 2005, 44, 6272. Coldham, I.; Hufton, R. Chem. Rev. 2005, 105, 2765. (d) Pandey, G.; Banerjee, P.; Gadre, S. R. Chem. Rev. 2006, 106, 4484. (e) Nair, V.; Suja, T. D. Tetrahedron 2007, 63, 12247.  1,3-Dipolar Addition via Iminium Catalysis Vicario, J. L.; Reboredo, S.; Badίa, D.; Carrillo, L. Chem. Int. Ed. 2007, 46, 5168; Ibrahem, I.; Rios, R.; Vesely, J.; Cordova, A. Tetrahedron. Lett. 2007, 48, 6252  Previous Representative Achievements

4. 4  1,3-Dipolar Addition by Bifunctional Catalyst  Previous Representative Achievements Xue, M.-X.; Zhang,X.-M.; Gong, L.-Z. SYNLETT 2008, 691-694 ; Liu, Y.-K.; Liu, H.; Du, W.; Yue, L.; Chen, Y.-C. Chem. Eur. J. 2008, 14, 9873.  Control of Stereochemistry with the Proposed Chiral BH-Bonded Dipole

5. 5 Up to 99% ee Gong, L. Z. J. Am. Chem. Soc. 2008, 130, 5652  Brønsted Acid-Catalyzed Asymmetric 1,3-Dipolar Cycloaddition Reaction

6. 6  Binaphthol-derived Bisphosphoric Acids

7. 7 entrycatalystsolventTemp ( o C)Yield (%)Ee (%) 11aCH 2 Cl 2 RT9698 21bCH 2 Cl 2 RT3392 31cCH 2 Cl 2 RT7945 41dCH 2 Cl 2 RT2710 51eCH 2 Cl 2 RT7423 61fCH 2 Cl 2 RT2676 71gCH 2 Cl 2 RT5059  Evaluation of the Catalysts

8. 8  The Reaction of Vinyl ketones and Esters entryR1R1 R2R2 R3R3 Time (h)Yield (%)ee (%) 14-NO 2 C 6 H 4 CH 3 H487796 24-CNC 6 H 4 CH 3 H744796 34-BrC 6 H 4 CH 3 H725895 44-ClC 6 H 4 CH 3 H746491 54-FC 6 H 4 CH 3 H724394 62-NO 2 C 6 H 4 CH 3 H648596 73-NO 2 C 6 H 4 CH 3 H746397 84-NO 2 C 6 H 4 OCH 3 H488295 92-NO 2 C 6 H 4 OCH 3 H729192 104-CNC 6 H 4 OCH 3 H6496 113-NO 2 C 6 H 4 OCH 3 H488497 124-BrC 6 H 4 OCH 3 H648097 134-NO 2 C 6 H 4 OCH 3 Ph488594 144-BrC 6 H 4 OCH 3 Ph728597 154-ClC 6 H 4 OCH 3 Ph726594 164-CNC 6 H 4 OCH 3 Ph727196 172-NO 2 C 6 H 4 OCH 3 Ph608598 Manusript in preparation

9. 9  Optimization of conditions for the reaction involving  -phenylglycine methyl ester

10. 10  Scope of Aldehydes entryR1R1 R2R2 R3R3 Yield (%) b ee (%) c 14-CF 3 C 6 H 4 CH 3 9894 24-BrC 6 H 4 CH 3 9397 34-ClC 6 H 4 CH 3 9694 44-FC 6 H 4 CH 3 8694 53-CNC 6 H 4 CH 3 6592 62-NO 2 C 6 H 4 CH 3 9896 72-BrC 6 H 4 CH 3 9691 82-Cl,4-FC 6 H 3 CH 3 9496 93-Cl,4-FC 6 H 3 CH 3 8788 104-Cl,3-FC 6 H 3 CH 3 8498 11c-C 6 H 11 CH 3 5875 12c-C 3 H 5 CH 3 6174 134-MeOPhCH=CHCH 3 96 144-NO 2 PhCH=CHCH 3 8998 154-NO 2 C 6 H 4 CH 3 C2H5C2H5 9592 164-NO 2 C 6 H 4 C2H5C2H5 CH 3 95 Manusript in preparation

11. 11  Scope of  -arylglycine methyl ester Manusript in preparation

12. 12  Scope of  -arylalanine methyl ester Manusript in preparation

13. 13 entryArYield (%)dree (%) 14-NO 2 C 6 H 4 828.5/197 24-BrC 6 H 4 8910/195 34-ClC 6 H 4 779/191 44-CNC 6 H 4 838/196 53-NO 2 C 6 H 4 809.5/197 62-NO 2 C 6 H 4 938/192  Generality for Fumarate Manusript in preparation

14. 14  Transition States Located by DFT Manusript in preparation

15. 15 Conclusion DFT 计算表明：双磷酸催化剂催化 的本体系的 1,3- 偶极环加成反应，经 历一种新型的双功能催化活化与立 体控制模式。  1.  2. Manusript in preparation

16. 16 致 谢  龚流柱 （教授）  西华师范大学化学化工学院  中国科学技术大学化学系