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hem., Int. Ed. 2007, 46(3): 389392. [53] Xie J. W., Yue L., Chen W., Du W., Zhu J., Deng J. G., Chen Y. C. Highly enantioselective michael addition of cyclic 1,3dicarbonyl pounds to α,βunsaturated ketones. Org. Lett. 2007, 9(3): 413415.[54] Moon H. W., Cho M. J., Kim D. Y. Enantioselective conjugate addition of fluorobis(phenylsulfonyl)methane toα,βunsaturated ketones catalyzed by chiral bifunctional organocatalysts. Tetrahedron Lett. 2009, 50(34): 4896–4898.[55] Dong L., Lu R., Du Q., Zhang J., Liu S., Xuan Y., Yan M.. Highly enantioselective conjugate addition of 1bromonitroalkanes to α,βunsaturated ketones catalyzed by 9amino9deoxyepiquinine. Tetrahedron 2009, 65(21): 41244129.[56] Tan B., Shi Z., Chua P. J., Zhong G. Organocatalytic Domino Double Michael Reaction: Efficient Synthesis of Multisubstituted Cyclopentanes. Org. Lett. 2008, 10(16): 34253428.[57] Tan B., Chua P. J., Li Y., Zhong G. MichaelHenry Reactions: A Highly Stereoselective Synthesis of Multifunctionalized Cyclohexanes with Two Quaternary Stereocenters. Org. Lett., 2008, 10(12): 24372440.[58] Tan B., Chua P. J., Zeng X., Lu M., Zhong G. A Highly Diastereo and Enantioselective Synthesis of Multisubstituted Cyclopentanes with Four Chiral Carbons by the Organocatalytic Domino MichaelHenry Reaction. Org. Lett. 2008, 10(16): 34893492.[59] McCooey S. H., Connon S. J. Readily Accessible 9epiamino Cinchona Alkaloid Derivatives Promote Efficient, Highly Enantioselective Additions of Aldehydes and Ketones to Nitroolefins. Org. Lett. 2007, 9(4): 599602.[60] Tan B., Zhang X., Chua P. J., Zhong G. Recyclable organocatalysis: highly enantioselective Michael addition of 1,3diaryl1,3propanedione to nitroolefins. Chem. Commun., 2009, 45(7): 779781.[61] Yue L., Du W., Liu Y. K., Chen Y. C. Organocatalytic Asymmetric Direct Michael Addition of Aromatic Ketones to Alkylidenemalononitriles. Tetrahedron Lett. 2008, 49(12) 38813884.[63] Yasuda K., Shindo M., Koga K. Enantioselective Michael reaction of ketone lithium enolates using a chiral amine ligand. Tetrahedron Lett. 1996, 37(35): 6343[63] Kang T. R., Xie J. W., Du W., Feng X., Chen Y. C. Stereoselective desymmetrisation of prochiral α,αdicyanoalkenes via domino Michael–Michael addition reactions. Org. Biomol. Chem., 2008, 6, 26732675.[64] Zhu Q., Cheng L., Lu Y. Asymmetric organocatalytic Michael addition of ketones to vinyl sulfone. Chem. Commun., 2008, 44(47): 6315–6317.[65] Li P., Wen S., Yu F., Liu Q., Li W., Wang Y., Liang X., Ye J. Enantioselective Organocatalytic Michael Addition of Malonates to α,βUnsaturated Ketones. Org. Lett., 2009, 11(3): 753756.[66] Wang J., Li H., Zu L., Jiang W., Xie H., Duan W., Wang W. Organocatalytic Enantioselective Conjugate Additions to Enones. J. Am. Chem. Soc. 2006, 128(39): 12652–12653.[67] Gu C. L., Liu L., Sui Y., Zhao J. L., Wang D., Chen Y. J. Highly enantioselective Michael additions of αcyanoacetate with chalcones catalyzed by bifunctional cinchonaderived thiourea organocatalyst. Tetrahedron: Asymmetry. 2007,18(4): 455–463.[68] Vakulya B., Varga S., Cs225。rgensen K. A. Organocatalytic Enantioselective Conjugate Addition to Alkynones. J. Am. Chem. Soc, 2004, 126(18): 5672–5673.[40] Sibi M. P., Manyem S. Enantioselective Conjugate Additions. Tetrahedron 2000, 56(11): 80338061.[41] Ono, N. In The Nitro Group in Organic Synthesis. WileyVCH: Weinheim, 2001, 159171.[42] Berner, O. M.。ngstr246。nge zwischen dem r228。 M228。 N225。 Tan, . Chiral Bicyclic Guanidine Catalyzed Enantioselective Reactions of Anthrones. J. Am. Chem. Soc. 2006, 128(4): 13692–13693.[19] Almasi, D.。 Fu, X.。 Goh, .。 Moisan, L. In the Golden Age of Organocatalysis. Angew. Chem. Int. Ed. 2004, 43(39): 5138 – 5175.[8] Corey E. J. Zhang F. Y. Mechanism and conditions for highly enantioselective epoxidation of α,βenones using chargeaccelerated catalysis by a rigid quaternary ammonium salt. Org. Lett. 1999, 1(8): 12871290.[9] Bernardi L., Jorgensen K. A. Enantioselective chlorination and fluorination of βketo phosphonates catalyzed by chiral Lewis acids. Chem. Commun. 2005, 41(10): 13241326.[10] Doyle A. G., Jacobsen E. N. SmallMolecule HBond Donors in Asymmetric Catalysis. Chem. Rev. 2007, 107(12), 57135743.[11] Bartoli G., Bosco M., Carlone A., Locatelli M., Melchiorre P., Sambri L. Organocatalytic Asymmetric αHalogenation of 1,3Dicarbonyl Compounds. Ang. Chem. Int. Ed. 2005, 44(38): 62196222.[12] Marckwald, W. Ueber asymmetrische Synthese. Ber. 1904 37(2): 13681370. [13] Houk K. N., Benjamin List B. Asymmetric Organocatalysis. Acc. Chem. Res. 2004, 37(8): 487.[14] Benaglia M., Puglisi A., Cozzi F. PolymerSupported Organic Catalysts. Chem. Rev. 2003, 103(9): 34013429.[15] Dalko P. I., Moisan L. Enantioselective Organocatalysis. Angew. Chem. Int. Ed. 2001, 40(20), 3726–3748.[16] List B., Lerner R. A., Barbas III C. F. Proline catalyzed direct asymmetric aldol reactions. J. Am. Chem. Soc. 2000, 122(10): 23952396.[17] Verkade J. M. M., van Hemert L. J. C., Quaedflieg P. J. L. M., Rutjes F. P. J. T. Organocatalysed asymmetric Mannich reactions. Chem. Soc. Rev. 2008, 37(1): 29–41.[18] Shen, J.。圖 吡咯里西啶生物堿與金雞納生物堿結(jié)構(gòu)的比較參考文獻(xiàn)[1] Jeffrey N. C. Rene H. Jennifer W. Sedative and anxiolytic effects of zopiclone39。因此,本文通過(guò)對(duì)植物原料中吡咯里西啶類生物堿的提取,進(jìn)而探索該類生物堿催化不對(duì)稱有機(jī)反應(yīng)的催化性能。吡咯里西啶生物堿在自然界大量存在,來(lái)源較廣,結(jié)構(gòu)類型多,有400多種,含有多個(gè)立體中心和官能團(tuán),從中尋找適合于某些不對(duì)稱有機(jī)反應(yīng)的有機(jī)小分子催化劑具有可行性。目前所采用的不對(duì)稱有機(jī)小分子催化劑的種類仍然十分稀少,大多數(shù)不對(duì)稱有機(jī)小分子催化劑即使通過(guò)結(jié)構(gòu)修飾也只能催化一些機(jī)理類似的少數(shù)幾種反應(yīng)。因此對(duì)手性有機(jī)小分子催化劑的研究越來(lái)越多地受到人們的重視。例如它們可以催化不對(duì)稱羥醛縮合反應(yīng)、不對(duì)稱Michael加成反應(yīng)、不對(duì)稱DielsAlder反應(yīng)等。所以,設(shè)計(jì)和開(kāi)發(fā)更多高效的金雞納生物堿衍生的有機(jī)分子催化劑,仍然是有機(jī)化學(xué)家面臨的熱點(diǎn)問(wèn)題之一。同時(shí),許多工