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化学应用与污染控制技术重点实验室年会 , 2010 , 12 , 12. Br ø nsted Acid-Catalyzed Asymmetric Three-Component 1,3-Dipolar Cycloaddition Reaction. 何 龙. 西华师范大学化学化工学院. The Importance of Pyrrolidine in Natural and Unnatural Biologically Active Products. Previous Representative Achievements.
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化学应用与污染控制技术重点实验室年会,2010,12,12化学应用与污染控制技术重点实验室年会,2010,12,12 Brønsted Acid-Catalyzed Asymmetric Three-Component 1,3-Dipolar Cycloaddition Reaction 何 龙 西华师范大学化学化工学院
The Importance of Pyrrolidine in Natural and Unnatural Biologically Active Products
Previous Representative Achievements • 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 • 1,3-Dipolar Addition by Bifunctional Catalyst 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
Brønsted Acid-Catalyzed Asymmetric 1,3-Dipolar Cycloaddition Reaction Up to 99% ee Gong, L. Z. J. Am. Chem. Soc. 2008, 130, 5652
The Reaction of Vinyl ketones and Esters Manusript in preparation
Optimization of conditions for the reaction involving a-phenylglycine methyl ester
Scope of Aldehydes Manusript in preparation
Scope of a-arylglycine methyl ester Manusript in preparation
Scope of a-arylalanine methyl ester Manusript in preparation
Generality for Fumarate Manusript in preparation
Transition States Located by DFT Manusript in preparation
Conclusion • 1. • 2. 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。 Manusript in preparation
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