脯氨酸二肽类手性催化剂的合成、固载及其应用研究
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摘要
有机催化剂催化的不对称合成反应是近年迅速发展起来的一个研究领域,设计、合成具有高活性、高选择性、可以循环利用的有机催化剂是该领域的前沿。
本文以天然的手性氨基酸为原料,经保护、酰胺化、脱保护等6步反应合成出9个末端带吡啶环的二肽衍生物,又以4-羟基-L-脯氨酸为原料合成二肽催化剂,然后以4位羟基为活性位点通过和三乙氧基硅基丙基异氰酸酯反应将催化剂固载到硅胶上,固载量为0.43mmol/g,从而对固载催化剂的方法进行初步探讨研究,
采用本文合成的催化剂催化环己酮与芳香醛的不对称直接aldol反应,详细地考察了反应温度、溶剂、催化剂用量、添加剂等因素对反应活性和对映选择性的影响。研究结果表明催化剂表现出较好的催化活性和对映选择性,在优化的反应条件下,aldol产物的产率最高达96%,ee值最高可达94%,dr值最高>99:1。此类催化剂在环己酮与硝基苯乙烯的nitro-Michael,也表现出一定的的催化活性,产率最高达91%,dr值最高达99:1,ee最高达70%。
通过偶联反应将催化剂1固载到硅胶上,并将其用于催化环己酮和硝基苯甲醛的aldol反应,dr值最高达到90:10,ee最高76%。催化剂重复6次以上,催化活性几乎没有变化,为今后硅胶固载催化剂和催化剂的回收利用提供了经验借鉴。
本文在大量合成实验的基础上,归纳总结二肽衍生物的合成条件和方法,为新颖有机小分子催化剂的进一步合成奠定了基础,同时也为催化剂的固载提供了经验。
Organocatalysts have widely applications in the field of asymmetric synthesis, especially, enantioselective C-C bond forming reactions,such as aldol reaction, Michael reaction, etc. Recently, many researchers have focused on the design and synthesis of new and highly efficient organocatalysts
In this paper, we incorporated both prolinamide moieties and aminopyridine in one molecule could give the potential organocatalysts.Boc-1～Boc-9 (65%～92%,yield )were synthetized by mixed anhydride method or DCC condensation using N-Boc-L- proline N-Boc-4-OH-L-proline and Picolinamide respectively, Finally, the catalysts 1-9 were synthesized after being deprotected by TFA.
The aldol reaction is one of the most important organic reactions, because it is a carbon-carbon bond forming reaction which produces highly functionalized compounds with a pair of newly generated chiral centers. We first examined the ability of the catalysts 1-9 to promote the direct aldol reaction between cyclohexanone and 4-nitrobenzaldehyde under various conditions. Catalysts 1, 4 and 9 are identified as the best catalysts for this reaction which lead to aldol adduct with excellent enantioselectivity and ee value up to 96%, dr value upto >99:1.
The reactions of different aromatic aldehydes with cyclohexanone were studied under the optimized conditions (using 20 mol% of 1 as catalyst in CHCl3). The reactions of different aromatic aldehydes, which bear an electron-withdrawing group on the benzene ring, proceeded smoothly in excellent enantioselectivities (ee 94%, dr> 99:1) to furnish the aldol adducts. In addition, halogenated benzaldehydes led to decreased yields. Interestingly, the ee values of the products remained at good levels. On the other hand, this catalytic system was proven to be completely ineffective for the aromatic aldehydes with an electron-donating group or without any substitution.
The Michael reaction is also an important C-C bond forming reaction in organic synthesis. We investigated the application of catalysts 1, 4and 9 for the Michael reaction between cyclohexanone and trans-β-nitrostyrene under the optimized reaction conditions. In the presence of 10 mol% catalyst loading, catalysts 1, 4 and 9 gave the product of cyclohexanone reacting with trans-β-nitrostyrene in moderate yield (up to 91% yield) and high diastereoselectivity( dr up to 99:1), but poor poor to moderate enantioselectivity( up to 70%, ee).
The catalyst 1 was supported using Mesoporous-silica. We first examined the ability of the catalyst to promote the direct aldol reaction between acetone and 4-nitrobenzaldehyde under various conditions. Resultly, The catalyst had moderater catalytic activity ( ee 76, dr 90:10). The supported catalyst could be easily separated from the reaction system by filtration and reused at least six times without significant lost of activity and enantioselectivity.
Via the researching work of this dissertation, suggest a new strategy in the design of new organocatalystss for direct asymmetric aldol reactions and related reactions and make the design and synthesis of catalyst possible to multiple reactions. While, our work provide experience for silica supported organocatalyst.
本文以天然的手性氨基酸为原料,经保护、酰胺化、脱保护等6步反应合成出9个末端带吡啶环的二肽衍生物,又以4-羟基-L-脯氨酸为原料合成二肽催化剂,然后以4位羟基为活性位点通过和三乙氧基硅基丙基异氰酸酯反应将催化剂固载到硅胶上,固载量为0.43mmol/g,从而对固载催化剂的方法进行初步探讨研究,
采用本文合成的催化剂催化环己酮与芳香醛的不对称直接aldol反应,详细地考察了反应温度、溶剂、催化剂用量、添加剂等因素对反应活性和对映选择性的影响。研究结果表明催化剂表现出较好的催化活性和对映选择性,在优化的反应条件下,aldol产物的产率最高达96%,ee值最高可达94%,dr值最高>99:1。此类催化剂在环己酮与硝基苯乙烯的nitro-Michael,也表现出一定的的催化活性,产率最高达91%,dr值最高达99:1,ee最高达70%。
通过偶联反应将催化剂1固载到硅胶上,并将其用于催化环己酮和硝基苯甲醛的aldol反应,dr值最高达到90:10,ee最高76%。催化剂重复6次以上,催化活性几乎没有变化,为今后硅胶固载催化剂和催化剂的回收利用提供了经验借鉴。
本文在大量合成实验的基础上,归纳总结二肽衍生物的合成条件和方法,为新颖有机小分子催化剂的进一步合成奠定了基础,同时也为催化剂的固载提供了经验。
Organocatalysts have widely applications in the field of asymmetric synthesis, especially, enantioselective C-C bond forming reactions,such as aldol reaction, Michael reaction, etc. Recently, many researchers have focused on the design and synthesis of new and highly efficient organocatalysts
In this paper, we incorporated both prolinamide moieties and aminopyridine in one molecule could give the potential organocatalysts.Boc-1～Boc-9 (65%～92%,yield )were synthetized by mixed anhydride method or DCC condensation using N-Boc-L- proline N-Boc-4-OH-L-proline and Picolinamide respectively, Finally, the catalysts 1-9 were synthesized after being deprotected by TFA.
The aldol reaction is one of the most important organic reactions, because it is a carbon-carbon bond forming reaction which produces highly functionalized compounds with a pair of newly generated chiral centers. We first examined the ability of the catalysts 1-9 to promote the direct aldol reaction between cyclohexanone and 4-nitrobenzaldehyde under various conditions. Catalysts 1, 4 and 9 are identified as the best catalysts for this reaction which lead to aldol adduct with excellent enantioselectivity and ee value up to 96%, dr value upto >99:1.
The reactions of different aromatic aldehydes with cyclohexanone were studied under the optimized conditions (using 20 mol% of 1 as catalyst in CHCl3). The reactions of different aromatic aldehydes, which bear an electron-withdrawing group on the benzene ring, proceeded smoothly in excellent enantioselectivities (ee 94%, dr> 99:1) to furnish the aldol adducts. In addition, halogenated benzaldehydes led to decreased yields. Interestingly, the ee values of the products remained at good levels. On the other hand, this catalytic system was proven to be completely ineffective for the aromatic aldehydes with an electron-donating group or without any substitution.
The Michael reaction is also an important C-C bond forming reaction in organic synthesis. We investigated the application of catalysts 1, 4and 9 for the Michael reaction between cyclohexanone and trans-β-nitrostyrene under the optimized reaction conditions. In the presence of 10 mol% catalyst loading, catalysts 1, 4 and 9 gave the product of cyclohexanone reacting with trans-β-nitrostyrene in moderate yield (up to 91% yield) and high diastereoselectivity( dr up to 99:1), but poor poor to moderate enantioselectivity( up to 70%, ee).
The catalyst 1 was supported using Mesoporous-silica. We first examined the ability of the catalyst to promote the direct aldol reaction between acetone and 4-nitrobenzaldehyde under various conditions. Resultly, The catalyst had moderater catalytic activity ( ee 76, dr 90:10). The supported catalyst could be easily separated from the reaction system by filtration and reused at least six times without significant lost of activity and enantioselectivity.
Via the researching work of this dissertation, suggest a new strategy in the design of new organocatalystss for direct asymmetric aldol reactions and related reactions and make the design and synthesis of catalyst possible to multiple reactions. While, our work provide experience for silica supported organocatalyst.
引文
[1]邢其毅,徐瑞秋,周政,裴伟伟,基础有机化学(第二版),北京:高等教育出版社,1993
[2]林国强,李月明,陈耀全,陈新滋,手性合成—不对称反应及其应用,北京:科学出版社,2005
[3] Dalko, P. L.; Moisan, L.“Enantioselective organocatalysis”, Angew Chem., Int. Ed. 2001, 40,3726-3748.
[4]张生勇,郭建全,不对称催化反应—原理及在有机合成中的应用,北京:科学出版社,2002
[5]尤大耙,手性化合物的现代研究方法,合肥:中国科学技术大学出版社, 1993
[6]殷元骐,蒋耀忠,不对称催化反应进展,北京:科学出版社,2000
[7] JARVO,E.R.; MILLER, S.J.“Amino acids and peptides as asymmrtric organocatalysis”,Tetrahedron 2002,58, 2481-2495.
[8] GRǒGER, H., WIKEN, J.“The application of L-proline as an enzyme mimic and further new asymmetric syntheses using small organic molecules as chiral catalysts”, Angew. Chem. Int. Ed 2001, 40,529-532.
[9] LIST, B.; LERNER, R. A.; BARBAS, C. F.,“III. Proline-catalyzed direct asymmetric aldol reactions”, J. Am. Chem. Soc. 2000, 122, 2395-2396
[10] LIST, B.“Asymmetric Aminocatalysis”, Synlett. 2001, 1675-1686
[11] LIST, B.“Proline-catalyzed asymmetric reactions”, Tetrahedron. 2002, 58, 5573-5590
[12] LIST, B.“Enamine catalysis is a powerful strategy for the catalytic generation and use of carbanion equivalents”, Acc. Chem. Res. 2004, 37, 548-557
[13] SEAYAD, J.; LIST, B.“Asymmetric Organocatalysis”, Org. Biomol. Chem. 2005, 3, 719-724
[14] LIST, B.“The ying and yang of asymmetric aminocatalysis”, Chem.Commun.2006. 8. 819-824
[15] SAKTHIVEL, K.; NOTZ, W.; BUI, T.; BARBAS, C. F., III.“Amino acidcatalyzed direct asymmetric aldol reactions: A bioorganic approach to catalytic asymmetric carbon-carbon bond-forming reactions”, J. Am. Chem. Soc. 2001, 123, 5260-5267
[16] NOTZ, W.; TANAKA, F.; BARBAS, C. F., III.“Enamine-based organocatalysis with proline and diamines: the development of direct catalytic asymmetric Aldol, Mannich, Michael and Diels-Alder reactions”, Acc. Chem. Res. 2004, 37, 580-591
[17] NORTHRUP, A. B.; MACMILLAN, D. W. C.“The first direct and enantioselective cross-aldol reaction of aldehydes”, J. Am. Chem. Soc. 2002, 124, 6798-6799
[18] NORTHRUP, A. B.; MACMILLAN, D. W. C.“Two-step synthesis of carbohydrates by selective aldol reactions”, Science. 2004, 305, 1752-1755
[19] SAITO, S.; YAMAMOTO, H.“Design of acid-base catalysis for the asymmetric direct aldol reaction”, Acc. Chem. Res. 2004, 37, 570-579
[20] NAKADAI, M.; SAITO, S.; YAMAMOTO, H.“Diversity-based strategy for discovery of environmentally benign organocatalyst: diamine-protonic acid catalysts for asymmetric direct aldol reaction”, Tetrahedron. 2002, 58, 8167-8177
[21]江焕峰,王玉刚,刘海灵,刘鹏.“非金属有机催化剂及其在有机化学反应中的应用”,有机化学. 2004, 24, 1513-1531
[22]傅滨,肖玉梅,覃兆海,董燕红,李楠.“有机催化剂在不对称合成中的应用”,有机化学. 2006, 26, 899-905
[23] TANG, Z.; JIANG, F.; YU, L.-T.; CUI, X.; GONG, L.-Z.; MI, A.-Q.; JIANG, Y.-Z.; WU, Y.-D.“Novel small organic molecules for a highly enantioselective direct aldol reaction”, J. Am. Chem. Soc. 2003, 125, 5262-5263
[24] TANG, Z.; YANG, Z.-H.; CHEN, X.-H.; CUN,L.-F.; MI, A.-Q.; JIANG, Y.-Z.; GONG, L.-Z.“A highly efficient organocatalyst for direct aldol reactions of ketones with aldedydes”, J. Am. Chem. Soc. 2005, 127, 9285-9289
[25] LUO, S. Z.; MI, X. L.; ZHANG, L.; LIU, S.; XU, H.; CHENG,J.-P.“Functionalized chiral ionic liquids as highly efficient asymmetric organocatalysts for Michael addition to nitroolefins”, Angew. Chem., Int. Ed. 2006, 45, 3093-3097
[26] LUO, S. Z.; XU, H.; LI J.-Y.; ZHANG, L.; CHENG, J.-P.“A simple primary-tertiary diamine-Br?nsted acid catalyst for asymmetric direct aldol reactions of linear aliphatic ketones”, J. Am. Chem. Soc. 2007, 129, 3074-3075
[27] DALKO, P. L.; MOISAN, L.“In the Golden Age of Organocatalysis”, Angew. Chem., Int. Ed. 2004, 43, 5138-5175
[29]李经纬,徐利文,夏春谷.“脯氨酸催化剂在不对称反应中的研究进展”,有机化学. 2004, 24, 23-28
[30]魏晓芳.“光学活性脯氨酸催化的不对称有机合成反应”,有机化学. 2005, 25, 1619-1625
[31] MACHAJEWSKI, T. D.; WONG, C. H.“The catalytic asymmetri aldol reaction”, Angew. Chem., Int. Ed. 2000, 39, 1352-1374
[32] ALCAIDE, B.; ALMENDROS, P.“The Direct Catalytic Asymmetric Aldol Reaction”, Eur. J. Org. Chem. 2002, 1595-1601
[33] MESTRES, R.“A green look at the aldol reaction”, Green Chem. 2004, 6, 583-603
[34] PALOMO, C.; OIARBIDE, M.; GARCíA, J. M.“Current progress in the asymmetric aldol addition reaction”, Chem. Soc. Rev. 2004, 33, 65-75
[35]姜丽娟,张兆国.“有机小分子催化的不对称羟醛缩合反应”,有机化学. 2006, 26, 618-626
[36] MUKAIYAMA, T.“The unexpected and the unpredictable in organic synthesis”, Tetrahedron. 1999, 55, 8609-8670
[37]樊建芬,孙云鹏,肖鹤鸣.“脯氨酸催化不对称羟醛缩合反应机理研究进展”,有机化学. 2006,26,1463-1467
[38] EDER, U.; SAUER, G.; WEICHENT, R. Angew. Chem. Int. Ed. 1971, 10, 496-497
[39] HAJOS, Z. G.; PARRISH, D. R.“Asymmetric synthesis of bicyclicintermediates of natural product chemistry”, J. Org. Chem. 1974, 39, 1615-1621
[40] NOTZ, W.; LIST, B .“Catalytic asymmetric synthesis of anti-1,2-diols”. J. Am. Chem. Soc. 2000, 122, 7386-7387.
[41] SAKTHIVEL , K.; NOTZ, W.; BUI, T.; BARBAS , C. F., III.“Amino acid catalyzed direct asymmetric aldol reactions : abioorganic approach to catalytic asymmetric carbon-carbon bond-forming reactions”J .Am Chem. Soc. 2001, 123, 5260-5267
[42] LIST, B., POJARLIEV, P.; CASTELLO, CASTELLO,“proline-catalyzed asymmetric aldol reactions between ketones andα-unsubstituted aldehydes”. Org. Lett. 2001, 3, 573-575.
[43] NORTHRUP, A. B.; MACMILLAN, D. W. C.“The first Direct and Enantioselective Cross-Aldol Reaction of Aldehydes”, J. Am. Chem. Soc. 2002, 124, 6798-6799
[44] NORTHPUP, A.B.; MACMILLAN, D. W. C.“Two-tep synthesis of carbohydrates by selective aldol reactions”. Science. 2004, 305, 1752-1755
[45] KOTRUSZ, P.; KMENTOVá, I.; GOTOV, B.; TOMA, ?.; SOL?áNIOVá, E.“Proline-catalysed sdymmetric aldol reaction in the room temperature ionic liquid [bmim] PF6”, Chem. Commun. 2002, 2510-2511
[46] GUO, H.-M.; CUN, L.-F.; GONG, L.-Z.; MI, A.-Q.; JIANG, Y.-Z.“Asymmetric direct aldol reaction catalyzed by an L-prolinamide derivative: considerable improvement of the catalytic efficiency in the ionic liquid”, Chem. Commun. 2005, 1450-1452
[47] CHANDRASEKHAR, S.; NARSEHMULU, C.; REDDY, N. R.; SULTANA, S. S.“Asymmetric aldol reactions in poly(ethylene glycol) catalyzed by L-proline”. Tetrahedron Lett. 2004, 45, 4581-4582
[48] CHANDRASEKHAR, S.; REDDY, N. R.; SULTANA, S. S.; NARSIHMULU, C.; REDDY, K. R.“L-proline catalysed asymmetric aldol reaction in PEG-400 as recyclable medium and transfer aldol reactions”, Tetrahedron. 2006, 62, 338-345
[49] NYBERG, A. I.; USANO, A.; PIHKO, P. M.“Proline-catalyzed ketone-aldehydealdol reactions are accelerated by water”, Synlett. 2004, 1891-1896
[50] PIHKO, P. M. LAURIKAINEN, K. M.; USANO, A.; NYBERG, A. I.;KAAVI, J. A.“Effect of additives on the proline-catalyzed ketone-aldehyde aldol reactions”, Tetrahedron. 2006, 62, 317-328
[51] WU, Y.-S.; CHEN, Y.; DENG, D.-S.; CAI, J.-W.“Proline-catalyzed asymmetric direct aldol reaction assisted by D-camphorsulfonic acid in aqueous media”, Synlett. 2005, 1627-1629
[52] ZHOU, Y.; SHAN, Z.-X.“(R) or (S)-Bi-2-naphthol assisted, L-proline catalyzed direct aldol reaction”, Tetrahedron: Asymmetry. 2006, 17, 1671-1677
[53] ZHOU, Y.; SHAN, Z.-X.“Chiral diols: new class of additives for direct aldol reaction catalyzed by L-proline”, J. Org. Chem. 2006, 71, 9510-9512
[54] HE, L.; JIANG, J.; TANG, Z.; CUI, X.; MI, A.-Q.; JIANG, Y.-Z.; GONG, L.-Z.“Highly diastereo- and enantioselective direct aldol reactions of cycloketones with aldehydes catalyzed by a trans-4-tert butyldimethylsiloxy-L-proline amide”, Tetrahedron: Asymmetry. 2007, 18, 265-270
[55] XU, X. Y.; TANG, Z.; WANG Y. Z.; LUO, S. W.; CUN, L. F.; GONG, L. Z.,“Asymmetric Organocatalytic direct Aldol Reactions of Ketones with Keto Acids and Their Application to the Synthesis of2-Hydroxy-?-butyrolactones”, J. Org. Chem. 2007, 72, 9905-9913
[56] RAJ, M.; VIUMAYA.; GINOTRA, S. K.; SINGH, V. K.;“Highly Enantioselective Direct AldolReaction Catalyzed by Organic Molecules”, Org. Lett. 2006. 8. 4097-4099.
[57] GRUTTADAURIA, M.; GIACALONE, F.; MARCULES, A. M.; NOTOA, R.;“Novel Prolinamide-Supported Polystyrene as Highly Stereoselective and Recyclable Organocatalyst for the Aldol Reaction”. Adv. Synth. Catal. 2008, 350, 1397-1405
[58] SCHWAB, R. S.; GALETTO, F. Z.; AZEREDO, J. B.; BRAGA, A. L.; LüDTKE, D. S.; PAIXǎO, M. W.;“Organocatalytic asymmetric aldol reactions mediated by acysteine-derived prolinamide”Tetrahedron Letters. 2008, 49, 5094–5097.
[59] HE, L.; JIANG, J.; TANG, Z.; CUI, X.; MI, A. Q.; JIANG, Y. Z.; GONG, L. Z.“Highly diastereo- and enantioselective direct aldol reactions of cycloketones with aldehydes catalyzed by a trans-4-tert butyldimethylsiloxy-L-proline amide”, Tetrahedron: Asymmetry. 2007, 18, 265-270
[60] TANIMORI, S.; NAKA, T.; KIRIHATA, M.“Synthesis of a new proline-derived organic catalyst and its evaluation for direct aldol reaction”, Synth. Commun. 2004, 34, 4043-4048
[61] CHEN, J. R.; LU, H. H.; LI, X. Y.; CHENG, L.; WAN, J.; XIAO, W. J.“Readily tunable and bifunctional L-prolinamide derivatives: design and application in the direct enantioselective aldol reactions”, Org. Lett. 2005, 7, 4543-4545
[62] SAMANTA, S.; LIU, J.; DOODA, R.; ZHAO, C. G.“C2-Symmetric bisprolin -amide as a highly efficient catalyst for direct aldol reaction”, Org. Lett. 2005, 7, 5321-5323
[63] CHENG, C. L.; SUN, J., WANG, C.; ZHANG, Y.; WEI, S. Y.; JIANG, F.; WU, Y. D.“Protonated N’-benzyl-N’-prolyl proline hydrazide as highly enantioselective catalyst for direct asymmetric aldol reaction”, Chem. Commun. 2006,2, 215-217
[64] CHEN, J. R.; LI, X. Y.; XING, X. N.; XIAO, W. J.“Sterically and electronically tunable and bifunctional organocatalysts: design and application in asymmetric aldol reaction of cyclic ketones with aldehydes”, J. Org. Chem. 2006, 71, 8198-8202
[65] FU, Y Q.; LI, Z.C., DING, L.N.; TAO, J.C.; ZHANG S.-H.; TANG, M.-S.“Direct asymmetric aldol reaction catalyzed by simple prolinamide phenols”, Tetrahedron: Asymmetry. 2006, 17, 3351-3357
[66]丁一,张雅文,刘艳华,罗晓清,马济美,沈宗旋.“N-[(S)-脯氨酰]羟胺的合成及催化直接不对称羟醛反应研究”,有机化学, 2005, 5, 567-569
[67] JIANG M., ZHU, S. F.; YANG, Y.; GONG, L. Z.; ZHOU, X. G.; ZHOU, Q. L.“Asymmetric aldol reactions catalyzed by new spiro diamine derivatives“, Tetrahedron: Asymmetry. 2006, 17, 384
[68] GUILLENA, G.; HITA, M. C.; NáJERA, C.“BINAM-prolinamides as recoverable catalysts in the direct aldol condensation”, Tetrahedron: Asymmetry. 2006, 17, 729-733
[69] GUILLENA, G.; HITA, M. C.; NáJERA, C.“Organocatalyzed direct aldol condensation using L-proline and BINAM-prolinamides: regio-, diastereo-, and enantioselective controlled synthesis of 1,2-diols”, Tetrahedron: Asymmetry. 2006, 17, 1027-1031
[70] GRYKO, D.; KOWALCZYK, B.; ZAWADZKI, ?.“Bisprolinediamides with the binaphthyl backbone as organocatalysts for the direct asymmetric aldol reaction”, Synlett. 2006, 1059-1062
[71] GUIZZETTI, S.; BENAGLIA, M.; PIGNATARO, L.; PUGLISI, A.“A multifunctional proline- based organic catalyst for enantioselective aldol reaction”, Tetrahedron: Asymmetry 2006, 17, 2754-2760
[72] GRYKO, D.; LIPI?SKI, R.“Asymmetric direct aldol reaction catalysed by L-prolinethioamides”, Eur. J. Org. Chem. 2007, 3864-3876
[73] GRYKO, D.; LIPI?SKI, R.“L-Prolinethioamides-efficient organocatalysts for the direct asymmetric aldol reaction”, Adv. Synth. Catal. 2005, 347, 1948-1952
[74] GRYKO, D.; ZIMNICKA, M.; LIPI?SKI, R.“Br?nsted acids as additives for the direct asymmetric aldol reaction catalyzed by L-prolinethioamides. direct evidence for enamine-iminium catalysis”, J. Org. Chem. 2007, 72, 964-970
[75] BERKESSEL, A.; KOCH, B.; LEX, J.“Proline-derived N-sulfonylcarboxamides: readily available, highly enantioselective and versatile catalysts for direct aldol reactions”, Adv. Synth. Catal. 2004, 346, 1141-1146
[76] COBB, A. J. A.; SHAW, D. M.; LONGBOTTOM, D. A.; LEY, S. V.“Organocatalysis with proline derivatives: improved catalysts for the asymmetric Mannich, nitro-Michael and aldol reactions”, Org. Biomol. Chem. 2005, 3, 84-96
[77] WU, Y. Y.; ZHANG,Y. Z.; YU, M.L.; ZHAO, G.; WANG, S.W.“Highly efficient and reusable dendritic catalysts derived from N-prolylsulfonamide for the asymmetric direct aldol reaction in water”, Org. Lett, 2006, 8, 4417-4420
[78] WANG, W.; MEI, Y.-J.; LI, H.; WANG, J.“A novel pyrrolidine imide catalyzed direct formation ofα,β-unsaturated ketones from unmodified ketones and aldehydes”, Org. Lett, 2005, 7, 601-604
[79] YANG, H.; CARTER, R. G.“N-(p-Dodecylphenylsulfonyl) -2-pyrrolidinecarb oxa -mide:A Practical Proline Mimetic for FacilitatingEnantioselective Aldol Reactions”. Org. Lett., 2008, 10, 4649-4652.
[80] GANDHI, S.; SINGH, V. K.“Synthesis of Chiral Organocatalysts derived from Aziridines: Application in Asymmetric Aldol Reaction”, J. Org. Chem., 2008, 73, 9411-9416.
[81] HARTIKKA, A.; ARVIDSSON, P. I.“Rational design of asymmetric organocatalysts increased reactivity and solvent scope with a tetrazolic acid”, Tetrahedron: Asymmetry 2004, 15, 1831-1834
[82] HARTIKKA, A.; ARVIDSSON, P. I.“5-(Pyrrolidin-2-yl)tetrazole: rationale for the increased reactivity of the tetrazole analogue of proline in organocatalyzed aldol reactions”, Eur. J. Org. Chem. 2005, 4287-4294
[83] ALEXANDER, J. A. C.; DEBORAH A. L.; DAVID M. S.; STEVEN V. L.“5-Pyrrolidin-2-yltetrazole as an asymmetric organocatalyst for the addition of ketones to nitro-olefins”, Chem. Commun. 2004, 1808-1809
[84] TORII, H.; NAKADAI, M.; ISHIHARA, K.; SAITO, S.; YAMAMOTO, H.“Asymmetric Direct Aldol Reaction Assisted by Water and a Proline-Derived Tetrazole Catalyst”, Angew. Chem., Int. Ed. 2004, 43, 1983-1986
[85] LACOSTE, E.; LANDAIS, Y.; SCHENK, K.; VERLHAC, J. B.; VINCENT, J. M.“Benzoimidazole-pyrrolidine (BIP), a highly reactive chiral organocatalyst for aldol process”, Tetrahedron Lett. 2004, 45, 8035-8038
[86] LACOSTE, E.; VAIQUE, E.; BERLANDE, M.; PIANET, I.; VINCENT, J. M.; LANDAIS, Y.“Benzoimidazole-pyrrolidine/H+ (BIP/H+), a highly reactive organocatalyst for asymmetric process”, Eur. J. Org. Chem. 2007, 167-177
[87] DICKERSON, T. J.; JANDA, K. D.“Aqueous Aldol Catalysis by a Nicotine Metabolite”, J. Am. Chem. Soc. 2002, 124, 3220-3221
[88] DICKERSON, T. J.; LOVRLL, T.; MEIJLER, M. M.; NOODLEMAN, L.; JANDA, K. D.“Nornicotine Aqueous Aldol Reactions: Synthetic and Theoretical Investigations into the Origins of Catalysis”, J. Org. Chem. 2004, 69, 6603-6609
[89] ZHENG, J. F.; LI, Y. X.; ZHANG, S. Q., YANG, S. T.; WANG, X. M.; WANG, Y. Z.; BAI, J.; LIU, F. A.“New N-terminal prolyl-dipeptide derivatives as organocatalysts”, Tetrahedron Letters, 2006 ,47 , 793-796.
[90] MASE, N.; NAKAI, Y.; OHARA, N.; YODA, H.; TAKABE, K.; TANAKA, F.; BARBAS, C. F., III.“Organocatalytic direct asymmetric aldol reactions in water”, J. Am. Chem. Soc. 2005, 124, 734-735
[91] MARTIN, H. J.; LIST, B.“Mining sequence space for asymmetric aminocatalysis: N-terminal prolyl-peptides efficiently catalyze enantioselective aldol and michael reactions”, Synlett. 2003, 1901-1902
[92] TANG, Z.; YANG, Z.H.; CUN, L. F.; GONG, L.Z.; MI, A.Q.; JIANG, Y. Z.“Small peptides catalyze highly enantioselective direct aldol reactions of aldehydes with hydroxyacetone: unprecedented regiocontrol in aqueous media”, Org. Lett. 2004, 6, 2285-2287
[93] KOFOED, J.; NIELSEN, J.; REYMOND, J. L.“Discovery of new peptide-based catalysts for the direct asymmetric aldol reaction”, Bioorg. Med. Chem. Lett. 2003, 13, 2445-2447
[94] TSOGOEVA, S. B.; WEI, S. W.“(S)-Histidine-based dipeptides as organic catalysts for direct asymmetric aldol reactions”, Tetrahedron: Asymmetry. 2005, 16, 1947-1951
[95] AKAGAWA, K.; SAKAMOTO, S.; KUDO, K.“Direct asymmetric aldol reaction in aqueous media using polymer-supported peptide”, Tetrahedron Lett. 2005, 46, 8185-8187
[96] KRATTIGER, P.; KOVASY, R.; REVELL, J. D.; IVAN, S.; WENNEMERS, H.“Increased structural complexity leads to higher activity: peptides as efficient and versatile catalysts for asymmetric aldol reactions”, Org. Lett. 2005, 7,1101-1103
[97] SHI, L. X.; SUN, Q.; GE, Z. M.; ZHU, Y. Q.; CHENG, T. M.; LI, R. T.“Dipeptide-catalyzed direct asymmetric aldol reaction”, Synlett. 2004, 2215-2217
[98] ANDREAE, M. R. M.; DAVIS, A. P.“Heterogeneous catalysis of the asymmetric aldol reaction by solid-supported proline-terminated peptides”, Tetrahedron: Asymmetry. 2005, 16, 2487-2492
[99] TSOGOEVA, S. B.; JAGTAP, S. B.; ARDEMASOVA, Z. A.“4-trans-Amino-proline based di- and tetrapeptides as organic catalysts for asymmetric C-C bond formation reactions”, Tetrahedron: Asymmetry. 2006, 17, 989-992
[100] ZOU, W.B.; IBRAHE, I.; DZIEDZIC, P.; SUNDEN, H.; CORDOVA, A.“Small peptides as modular catalysts for the direct asymmetric aldol reaction: ancient peptides with aldolase enzyme activity”, Chem. Commun. 2005, 4946-4948
[101] CORDOVA, A.; ZOU, W. B.; DZIEDZIC, P.; IBRAHEM, I.; REYES, E.; XU, Y. M.“Direct asymmetric intermolecular aldol reactions catalyzed by amino acids and small peptides”, Chem. Eur. J. 2006, 12, 5383-5397
[102] LUPPI, G.; COZZI, P. G.; MONARI, M.; KAPTEIN, B.; BROXTERMAN, Q. B.; TOMASINI, C.,“Dipeptide-Catalyzed Asymmetric Aldol Condensation of Acetone with (N-Alkylated) Isatins”, J. Org. Chem. 2005, 70, 7418-7421
[103] SHEN Z.X.; CHEN, W. H.; JIANG, H.; DING, Y.; LUO, X. Q.; ZHANG, Y. W.“Direct asymmetric aldol reactions catalyzed by (4R)-4-(b-naphtha lenyl) methoxy-(S)-proline”, Chirality. 2005, 17, 119-120
[104] SHEN Z. X.; MA, J. M.; LIU, Y. H.; JIAO, C. J.; LI, M.; ZHANG, Y. W.“β-Cyclodextrin-Immobilized(4S)-Phenoxy-(S)-proline as a Catalyst for Direct. Asymmetric Aldol Reactions”, Chirality. 2005, 17, 556-558
[105] FONT, D.; JIMENO, C.; PERICáS, M. A.“Polystyrene-supported Hydroxyproline: An Insoluble, Recyclable Organocatalyst for the Asymmetric Aldol Reaction in Water”, Org. Lett. 2006, 8, 4653-4655
[106] BELLIS, E.; KOKOTOS, G..“4-Substituted proline as organocatalysts for aldol reactions”, Tetrahedron. 2005, 61, 8669-8676
[107]BELLIS, E.; VASILATOU, K.; KOKOTOS, G.“4-Substituted prolyl sulfonamides as enantioselective organocatalysts for aldol reactions”, Synthesis. 2005, 2407-2411
[108]HAYASHI, Y. J.; ARATAKE, S.; OKANO, T.; TAKAHASHI, J.; SUMIYA, T.; SHOJI, M.“Combined proline–surfactant organocatalyst for the highly diastereo- and enantioselective aqueous direct cross-aldol reaction of aldehydes”, Angew. Chem., Int. Ed. 2006, 45, 5527-5529
[109] BENAGAIA, M.; CELENTANO, G.; COZZIA, F.“Enantioselective aldol condensations catalyzed by poly(ethylene glycol)-supported praline”, Adv. Synth. Catal. 2001, 343, 171-173
[110] MIAO, W. S.; CHAN, T. H.“Ionic-liquid-supported organocatalyst:efficient and recyclable ionic-liquid-anchored proline for asymmetric aldol reaction”, Adv. Synth. Catal. 2006, 348, 1711-1718
[111] LIU, Y. X.; SUN, Y. N., TAN, H. H.; TAO, J. C.“Asymmetric Aldol Reaction Catalyzed by New Recyclable Polystyrene-supported L-proline in the Presence of Water”, Catal Lett, 2008 , 120 , 281-287.
[112] GU, L. Q.; YU, M. L.; WU, X. Y.; ZHANG, Y. Z.; ZHAO, G.“4,4’-Disu bstituted L-prolines as highly enantioselective catalysts for direct aldol reactions”, Adv. Synth. Catal. 2006, 348, 2223-2228
[113] LIMBACH, M.“β-Homoamino acids as catalysts in enantioselective intra and intermolecular aldol reactions”, Tetrahedron Lett. 2006. 47. 3843-3847
[114] DAVIES, S. G.; SHEPPARD, RUTH, L.; SMITH, A. D.; THOMSON, J. E.“Highly enantio-selective organocatalysis of the Hajos–Parrish–Eder–Sauer– Wiechert reaction by theβ-amino acid cispentacin”, Chem. Commun. 2005, 3802-3804
[115] TANG, X. P.; LIéGAULT, B.; RENAUD, J. L.; BRUNEAU, C.“(S, S, S)- Perhy droindolic acid: efficient catalyst for direct asymmetric aldol reactionfrom aromatic aldehydes”, Tetrahedron: Asymmetry. 2006, 17, 2187-2190
[116] KANO, T.; TAKAI, J.; TOKUDA, O.;MARUOKA, K.“Design of an Axially Chiral Amino Acid with a Binaphthyl Backbone as an Organocatalyst for a Direct Asymmetric Aldol Reaction”, Angew. Chem. Int. Ed. 2005, 44, 3055-3057
[117] KANO, T.; TOKUDA, O.; MARUOKA, K.“Synthesis of a biphenyl-based axially chiral amino acid as a highly efficient catalyst for the direct asymmetric aldol reaction”, Tetrahedron Lett. 2006, 47, 7423-7426
[118] KANO, T.; TOKUDA, O.; TAKAI, J.; MARUOKA, K.“Design of a binaphthyl-based axially chiral amino acid as an organocatalyst for direct asymmetric aldol reactions”, Chem. Asian. J. 2006, 1–2, 210-215
[119] GU, Q.; WANG, X. F.; WANG, L.; WU, X.Y.; ZHOU, Q. L.“(2S, 5S)-Pyrrolidine-2, 5-dicarboxylic acid, an efficient chiral organocatalyst for direct aldol reaction”, Tetrahedron: Asymmetry. 2006, 17, 1537-1540
[120] DINéR, P.; AMEDJKOUH, M.“Aminophosphonates as organocatalysts in the direct asymmetric aldol reaction: towards syn selectivity in the presence of Lewis bases”, Org. Biomol. Chem. 2006, 4, 2091-2096
[121] CORDOVA, A.; NOTZ, W.; BARBAS, C. F., III.“Direct organocatalytic aldol reaction in buffered aqueous media”, Chem. Commun. 2002, 3024-3025
[122] PENG, Y. Y.; DING, Q. P.; LI, Z. C.; WANG, P. G.; CHENG, J.P.“Proline catalyzed aldol reaction in aqueous micelles: an environmentally friendly reaction system”, Tetrahedron Lett. 2003, 44, 3871-3875
[123] CODOVA, A.; ZOU, W.B.; IBRAHEM, I.; REYES, E.; ENGQVIST, M.; LIAO, W.W.“Acyclic amino acid-catalyzed direct asymmetric aldol reactions: alanine, the simplest stereoselective organocatalyst”, Chem. Commun. 2005, 3586-3588
[124] JIANG, Z.Q.; LIANG, Z.; WU, X.Y.; LU, Y. X.“Asymmetric aldol reaction catalyzed by tryptophan in water”, Chem. Commun. 2006, 2801-2803
[125] CHIMMI S. S.; MAHAJAN, D.; BABU, V. V. S.“Protonated chiral prolinamide catalyzed enantioselective direct aldol reaction in water”, Tetrahedron Lett.2005, 46, 5617-5619
[126] CHIMMI, S. S.; MAHAJAN, D.“Small organic molecule catalyzed enantioseletive direct aldol reaction in water”, Tetrahedron: Asymmetry. 2006, 17, 2108-2119
[127] HAYASHI, Y.; SUMIYA, T.; TAKAHASHI, J.; GOTOH, H.; URUSHIMA, T.; SHOJI, M.“Highly diastereo- and enantioselective direct aldol reactions in water”, Angew. Chem. Int. Ed. 2006, 45, 958-961
[128] PERLMUTTER, P.“Conjugate addition reactions in organic synhtesis“. Pergamon, Oxford. 1992.
[129] ROSSITER, B, E.; SWINGLE, N. M. Chem. Rev. 1992, 92, 771-806
[130] BERNER, O. M.; TEDESCHI, L.; ENDERS, D.“Asymmetric Michael Additions to Nitroalkenes”, Eur. J. Org. Chem. 2002, 1877-1894
[131] LIST, B.; POJARLIEV, P.; MARTIN, H. J.“Efficient proline-catalyzed michael additions of unmodified ketones to nitro olefins”, Org. Lett. 2001, 3, 2423-2425
[132] SAKTHIVEL, K.; NOTZ, W.; BUI, T.; BARBAS, C. F., III.“Amino Acid Catalyzed Direct Asymmetric Aldol Reactions: A Bioorganic Approach to Catalytic Asymmetric Carbon-Carbon Bond-Forming Reactions”J. Am. Chem. Soc. 2001, 123, 5260-5267
[133] RASALKAR, M. S.; POTDAR, M. K.; MOHILE, S. S.; SALUNKHE, M. M.“An ionic iquid influenced l-proline catalysed asymmetric Michael addition of ketones to nitrostyrene”. J. Mol. Catal. A 2005, 235, 267-270
[134] TERAKADO, D.; TAKANO, M.; ORIYAMA, T.“Highly Enantioselective (S)-Homoproline-catalyzed Michael Addition Reactions of Ketones toβ-Nitrostyrenes”, Chemistry Lett. 2005, 34, 962-963
[135] ZHU, M.K.; CUN, L. F.; MI, A.Q.; JIANG, Y.Z.; GONG, L.Z.“A highly enantioselective organocatalyst for the Michael addition of cyclic ketones to nitroolefins”, Tetrahedron: Asymmetry. 2006, 17, 491-493
[136] MASE, N.; WATANABER, KAORI.; YODA, H.; TAKABE, K.; TANAKA, F.; BARBAS, C. F. III.“Organocatalytic Direct Michael Reaction of Ketones andAldehydes withβ-Nitrostyrene in Brine”, J. Am. Chem. Soc. 2006, 128, 4966-4967
[137] PANSARE, S. V.; PANDYA, K.“Simple diamine- and triamine-protonic acid catalysts for the enantioselective michael addition of cyclic ketones to nitroalkenes”, J. Am. Chem. Soc. 2006, 128, 9624-9625
[138] VISHNUMAYA.; SINGH, V. K.“Highly enantioselective water-compatible organocatalyst for michael reaction of ketones to nitroolefins”, Org. Lett. 2007, 9, 1117-1119
[139] ANDREY, O.; ALEXAKIS, A.; TOMASSINI, A.; BERNARDINELLI, G.“The use of n-alkyl-2,2’-bipyrrolidine derivatives as organocatalysts for the asymmetric michael addition of ketones and aldehydes to nitroolefins”, Adv. Synth. Catal. 2004, 346, 1147-1168
[140] COBB, A. J. A.; LONGBOTTOM, D. A.; SHAW, D. M.; LEY, S. V.“5-Pyrrolidin-2-yltetrazole as an asymmetric organocatalyst for the addition of ketones to nitro-olefins”, Chem. Commun. 2004, 1808-1809
[141] MITCHELL, C. E. T.; COBB, A. J. A.; LEY, S. V.“A homo-proline tetrazole as an improved organocatalyst for the asymmetric michael addition of carbonyl compounds to nitro-olefins”, Synlett. 2005, 611-614
[142] WANG, W.; WANG, J.; LI, H.“Direct, highly enantioselective pyrrolidine sulfonamide catalyzed michael addition of aldehydes to nitrostyrenes”, Angew. Chem. Int. Ed. 2005, 44, 1369-1371
[143] ZU, L. S.; WANG, J.; LI, H.; WANG, W.“A recyclable fluorous (S)-pyrrolidine sulfonamide promoted direct, highly enantioselective michael addition of ketones and aldehydes to nitroolefins in water”, Org. Lett. 2006, 8, 3077-3079
[144] ISHII,T.; FUJIOKA, S.; SEKIGUCHI, Y.; KOTSUKI, H.“A new class of chiral pyrrolidine-pyridine conjugate base catalysts for use in asymmetric michael addition reactions”, J. Am. Chem. Soc. 2004, 126, 9558-9559
[145] LUO, S. Z.; XU, H.; MI, X. L.; LI, J. Y.; ZHENG, X. X.; CHENG, J. P.“Evolution of Pyrrolidine-Type Asymmetric Organocatalysts by“Click”Chemistry”, J. Org. Chem. 2006, 71, 9244-9247
[146] LUO, S. Z.; MI, X. L.; LIU, S.; XU, H.; CHENG, J. P.“Surfactant-type asymmetric organocatalyst: organocatalytic asymmetric Michael addition to nitrostyrenes in water”, Chem. Commun. 2006, 3687-3689
[147] ALMASI, D.; ALONSO, D. A.; NáJERA, C.“Enantioselective conjugate addition of ketones toβ-nitrostyrenes catalyzed by 1,2-amino alcohol-derived prolinamides”, Tetrahedron: Asymmetry. 2006, 17, 2064-2068
[148]PALOMO, C.; VERA, S.; MIELGO, A.; BENGOA, E. G.“Highly efficient asymmetric michael addition of aldehydes to nitroalkenes catalyzed by a simple trans-4-hydroxyprolylamide”, Angew. Chem. Int. Ed. 2006, 45, 5984-5987
[149] ALMASüI, D.; ALONSO, D. A.; NA′JERA, C.“Enantioselective conjugate addition of ketones toβ-nitrostyrenes catalyzed by 1,2-amino alcohol-derived prolinamides”Tetrahedron: Asymmetry 2006,17, 2064-2068
[150] CLARKE, M. L.; FUENTES, J. A.“Self- assembly of organocatalysts: fine-tuning organocatalytic reactions”, Angew. Chem. Int. Ed. 2007, 46, 930-933
[151] YALALOV, D. A.; TSOGOEVA, S. B.; SCHMATA, S.“Chiral Thiourea-Based Bifunctional Organocatalysts in theAsymmetric Nitro-Michael Addition: A Joint Experimental-Theoretical Study”AdV. Synth. Catal. 2006, 348, 826-832
[152] TSOGOEVA, S. B.; SHENG, W. W.,“Highly enantioselective addition of ketones to nitroolefins catalyzed by new thiourea–amine bifunctional organocatalysts”Chem. Commun. 2006, 1451-1453
[153] HUANG, H.; JACOBSEN, E. N.“Highly Enantioselective Direct Conjugate Addition of Ketones to Nitroalkenes Promoted by A Chiral Primary Amine-Thiourea Catalyst”. J. Am. Chem. Soc. 2006, 128, 7170-1771.
[154] CAO, C. L.; YE, M. C.; SUN, X. L.; TANG, Y.“Pyrrolidine-thiourea as a bifunctional organocatalyst: highly enantioselective michael addition of cyclohexanone to nitroolefins”, Org. Lett. 2006, 8, 2901-2904
[155] CAO, Y. J.; LAI, Y. Y.; WANG, X.; LI, Y. J.; XIAO, W. J.“Michael additions inwater of ketones to nitroolefins catalyzed by readily tunable and bifunctional pyrrolidine–thiourea organocatalysts”, Tetrahedron Lett. 2007, 48, 21-24
[156] LIU, K.; CUI, H. F.; NIE, J.; DONG, K.Y.; LI, X. J.; MA, J. A.“Highly Enantioselective michael addition of aromatic ketones to nitroolefins promoted by chiral bifunctional primary amine-thiourea catalysts based on saccharides”, Org. Lett. 2007, 9, 923-925
[157] MCCOEY, S. H.; CONNON, S. J.“Readily accessible 9-epi-amino cinchona alkaloid derivatives promote efficient, highly enantioselective additions of aldehydes and ketones to nitroolefins”, Org. Lett. 2007, 9, 599-602
[158] BENAGLIA, M.; CELENTANO, G.; COZZI, F.“Enantioselective Aldol Condensations Catalyzed by Poly(ethylene glycol)-Supported Proline”, Adv. Synth. Catal. 2001, 343, 171–173;
[159] BENAGLIA, M.; CINQUINI, M.; COZZI, F.; PUGLISIS, A.; CELENTANO, G.“Poly(Ethylene Glycol)-Supported Proline: AVersatile Catalyst for the Enantioselective Aldol and Iminoaldol Reactions”Adv. Synth.Catal. 2002, 344, 533–542.
[160] SALVADORI, P.; PINI, D.; PETRI, A. Synlett 1999, 1181–1190;
[161] SALUZZO, C.; HALLE, R.; TOUCHARD, F.; FACHE, F.; SCHULZ, E.; LEMAIRE, M. J.Organomet. Chem. 2000, 603, 30–39;
[162] CALDERO′N, F.; FERNA′NDEZ, R.; SANCHEZ, F.; MAYORALAS, A. F.“Asymmetric Aldol Reaction Using Immobilized Proline on Mesoporous Support”, Adv. Synth. Catal. 2005, 347, 1395–1403
[163] DOYAGU¨EZ, E. G.; CALDERO′N, F.; MAYORALAS, A. F.,“Asymmetric Aldol Reaction Catalyzed by a Heterogenized Proline on a Mesoporous Support. The Role of the Nature of Solvents”J. Org. Chem. 2007, 72,9353-9356.
[164] YAN, J.; WANG, L.,“Asymmetric Aldol Reactions Catalyzed by Efficient and Recyclable Silica-Supported Proline-Based Peptides”CHIRALITY, 2009, 21 413-420.
[165] OCHIAI E. Recent Japanese work on the chemistry of pyridine 1-oxide andrelated compounds [ J ]. J. Org. Chem, 1953, 18:534-551
[166]王志样,张志炳. 4-氨基吡啶合成的改进[J].中国医药工业杂志, 2001, 32 (2) : 83- 84.
[167]杨春常,范平,黄治清,等.对氨基吡啶的合成与研究[J].辽宁化工, 1991, 28 (3) : 36237.
[168] CHEN, F.B, SHI HUANG, H. Z., LIU, F.Y, PENG Y.G.,“Proline-based dipeptides with two amide units as organocatalyst for theasymmetric aldol reaction of cyclohexanone with aldehydes”. Tetrahedron 64, 2008, 17, 9585-9591.
[2]林国强,李月明,陈耀全,陈新滋,手性合成—不对称反应及其应用,北京:科学出版社,2005
[3] Dalko, P. L.; Moisan, L.“Enantioselective organocatalysis”, Angew Chem., Int. Ed. 2001, 40,3726-3748.
[4]张生勇,郭建全,不对称催化反应—原理及在有机合成中的应用,北京:科学出版社,2002
[5]尤大耙,手性化合物的现代研究方法,合肥:中国科学技术大学出版社, 1993
[6]殷元骐,蒋耀忠,不对称催化反应进展,北京:科学出版社,2000
[7] JARVO,E.R.; MILLER, S.J.“Amino acids and peptides as asymmrtric organocatalysis”,Tetrahedron 2002,58, 2481-2495.
[8] GRǒGER, H., WIKEN, J.“The application of L-proline as an enzyme mimic and further new asymmetric syntheses using small organic molecules as chiral catalysts”, Angew. Chem. Int. Ed 2001, 40,529-532.
[9] LIST, B.; LERNER, R. A.; BARBAS, C. F.,“III. Proline-catalyzed direct asymmetric aldol reactions”, J. Am. Chem. Soc. 2000, 122, 2395-2396
[10] LIST, B.“Asymmetric Aminocatalysis”, Synlett. 2001, 1675-1686
[11] LIST, B.“Proline-catalyzed asymmetric reactions”, Tetrahedron. 2002, 58, 5573-5590
[12] LIST, B.“Enamine catalysis is a powerful strategy for the catalytic generation and use of carbanion equivalents”, Acc. Chem. Res. 2004, 37, 548-557
[13] SEAYAD, J.; LIST, B.“Asymmetric Organocatalysis”, Org. Biomol. Chem. 2005, 3, 719-724
[14] LIST, B.“The ying and yang of asymmetric aminocatalysis”, Chem.Commun.2006. 8. 819-824
[15] SAKTHIVEL, K.; NOTZ, W.; BUI, T.; BARBAS, C. F., III.“Amino acidcatalyzed direct asymmetric aldol reactions: A bioorganic approach to catalytic asymmetric carbon-carbon bond-forming reactions”, J. Am. Chem. Soc. 2001, 123, 5260-5267
[16] NOTZ, W.; TANAKA, F.; BARBAS, C. F., III.“Enamine-based organocatalysis with proline and diamines: the development of direct catalytic asymmetric Aldol, Mannich, Michael and Diels-Alder reactions”, Acc. Chem. Res. 2004, 37, 580-591
[17] NORTHRUP, A. B.; MACMILLAN, D. W. C.“The first direct and enantioselective cross-aldol reaction of aldehydes”, J. Am. Chem. Soc. 2002, 124, 6798-6799
[18] NORTHRUP, A. B.; MACMILLAN, D. W. C.“Two-step synthesis of carbohydrates by selective aldol reactions”, Science. 2004, 305, 1752-1755
[19] SAITO, S.; YAMAMOTO, H.“Design of acid-base catalysis for the asymmetric direct aldol reaction”, Acc. Chem. Res. 2004, 37, 570-579
[20] NAKADAI, M.; SAITO, S.; YAMAMOTO, H.“Diversity-based strategy for discovery of environmentally benign organocatalyst: diamine-protonic acid catalysts for asymmetric direct aldol reaction”, Tetrahedron. 2002, 58, 8167-8177
[21]江焕峰,王玉刚,刘海灵,刘鹏.“非金属有机催化剂及其在有机化学反应中的应用”,有机化学. 2004, 24, 1513-1531
[22]傅滨,肖玉梅,覃兆海,董燕红,李楠.“有机催化剂在不对称合成中的应用”,有机化学. 2006, 26, 899-905
[23] TANG, Z.; JIANG, F.; YU, L.-T.; CUI, X.; GONG, L.-Z.; MI, A.-Q.; JIANG, Y.-Z.; WU, Y.-D.“Novel small organic molecules for a highly enantioselective direct aldol reaction”, J. Am. Chem. Soc. 2003, 125, 5262-5263
[24] TANG, Z.; YANG, Z.-H.; CHEN, X.-H.; CUN,L.-F.; MI, A.-Q.; JIANG, Y.-Z.; GONG, L.-Z.“A highly efficient organocatalyst for direct aldol reactions of ketones with aldedydes”, J. Am. Chem. Soc. 2005, 127, 9285-9289
[25] LUO, S. Z.; MI, X. L.; ZHANG, L.; LIU, S.; XU, H.; CHENG,J.-P.“Functionalized chiral ionic liquids as highly efficient asymmetric organocatalysts for Michael addition to nitroolefins”, Angew. Chem., Int. Ed. 2006, 45, 3093-3097
[26] LUO, S. Z.; XU, H.; LI J.-Y.; ZHANG, L.; CHENG, J.-P.“A simple primary-tertiary diamine-Br?nsted acid catalyst for asymmetric direct aldol reactions of linear aliphatic ketones”, J. Am. Chem. Soc. 2007, 129, 3074-3075
[27] DALKO, P. L.; MOISAN, L.“In the Golden Age of Organocatalysis”, Angew. Chem., Int. Ed. 2004, 43, 5138-5175
[29]李经纬,徐利文,夏春谷.“脯氨酸催化剂在不对称反应中的研究进展”,有机化学. 2004, 24, 23-28
[30]魏晓芳.“光学活性脯氨酸催化的不对称有机合成反应”,有机化学. 2005, 25, 1619-1625
[31] MACHAJEWSKI, T. D.; WONG, C. H.“The catalytic asymmetri aldol reaction”, Angew. Chem., Int. Ed. 2000, 39, 1352-1374
[32] ALCAIDE, B.; ALMENDROS, P.“The Direct Catalytic Asymmetric Aldol Reaction”, Eur. J. Org. Chem. 2002, 1595-1601
[33] MESTRES, R.“A green look at the aldol reaction”, Green Chem. 2004, 6, 583-603
[34] PALOMO, C.; OIARBIDE, M.; GARCíA, J. M.“Current progress in the asymmetric aldol addition reaction”, Chem. Soc. Rev. 2004, 33, 65-75
[35]姜丽娟,张兆国.“有机小分子催化的不对称羟醛缩合反应”,有机化学. 2006, 26, 618-626
[36] MUKAIYAMA, T.“The unexpected and the unpredictable in organic synthesis”, Tetrahedron. 1999, 55, 8609-8670
[37]樊建芬,孙云鹏,肖鹤鸣.“脯氨酸催化不对称羟醛缩合反应机理研究进展”,有机化学. 2006,26,1463-1467
[38] EDER, U.; SAUER, G.; WEICHENT, R. Angew. Chem. Int. Ed. 1971, 10, 496-497
[39] HAJOS, Z. G.; PARRISH, D. R.“Asymmetric synthesis of bicyclicintermediates of natural product chemistry”, J. Org. Chem. 1974, 39, 1615-1621
[40] NOTZ, W.; LIST, B .“Catalytic asymmetric synthesis of anti-1,2-diols”. J. Am. Chem. Soc. 2000, 122, 7386-7387.
[41] SAKTHIVEL , K.; NOTZ, W.; BUI, T.; BARBAS , C. F., III.“Amino acid catalyzed direct asymmetric aldol reactions : abioorganic approach to catalytic asymmetric carbon-carbon bond-forming reactions”J .Am Chem. Soc. 2001, 123, 5260-5267
[42] LIST, B., POJARLIEV, P.; CASTELLO, CASTELLO,“proline-catalyzed asymmetric aldol reactions between ketones andα-unsubstituted aldehydes”. Org. Lett. 2001, 3, 573-575.
[43] NORTHRUP, A. B.; MACMILLAN, D. W. C.“The first Direct and Enantioselective Cross-Aldol Reaction of Aldehydes”, J. Am. Chem. Soc. 2002, 124, 6798-6799
[44] NORTHPUP, A.B.; MACMILLAN, D. W. C.“Two-tep synthesis of carbohydrates by selective aldol reactions”. Science. 2004, 305, 1752-1755
[45] KOTRUSZ, P.; KMENTOVá, I.; GOTOV, B.; TOMA, ?.; SOL?áNIOVá, E.“Proline-catalysed sdymmetric aldol reaction in the room temperature ionic liquid [bmim] PF6”, Chem. Commun. 2002, 2510-2511
[46] GUO, H.-M.; CUN, L.-F.; GONG, L.-Z.; MI, A.-Q.; JIANG, Y.-Z.“Asymmetric direct aldol reaction catalyzed by an L-prolinamide derivative: considerable improvement of the catalytic efficiency in the ionic liquid”, Chem. Commun. 2005, 1450-1452
[47] CHANDRASEKHAR, S.; NARSEHMULU, C.; REDDY, N. R.; SULTANA, S. S.“Asymmetric aldol reactions in poly(ethylene glycol) catalyzed by L-proline”. Tetrahedron Lett. 2004, 45, 4581-4582
[48] CHANDRASEKHAR, S.; REDDY, N. R.; SULTANA, S. S.; NARSIHMULU, C.; REDDY, K. R.“L-proline catalysed asymmetric aldol reaction in PEG-400 as recyclable medium and transfer aldol reactions”, Tetrahedron. 2006, 62, 338-345
[49] NYBERG, A. I.; USANO, A.; PIHKO, P. M.“Proline-catalyzed ketone-aldehydealdol reactions are accelerated by water”, Synlett. 2004, 1891-1896
[50] PIHKO, P. M. LAURIKAINEN, K. M.; USANO, A.; NYBERG, A. I.;KAAVI, J. A.“Effect of additives on the proline-catalyzed ketone-aldehyde aldol reactions”, Tetrahedron. 2006, 62, 317-328
[51] WU, Y.-S.; CHEN, Y.; DENG, D.-S.; CAI, J.-W.“Proline-catalyzed asymmetric direct aldol reaction assisted by D-camphorsulfonic acid in aqueous media”, Synlett. 2005, 1627-1629
[52] ZHOU, Y.; SHAN, Z.-X.“(R) or (S)-Bi-2-naphthol assisted, L-proline catalyzed direct aldol reaction”, Tetrahedron: Asymmetry. 2006, 17, 1671-1677
[53] ZHOU, Y.; SHAN, Z.-X.“Chiral diols: new class of additives for direct aldol reaction catalyzed by L-proline”, J. Org. Chem. 2006, 71, 9510-9512
[54] HE, L.; JIANG, J.; TANG, Z.; CUI, X.; MI, A.-Q.; JIANG, Y.-Z.; GONG, L.-Z.“Highly diastereo- and enantioselective direct aldol reactions of cycloketones with aldehydes catalyzed by a trans-4-tert butyldimethylsiloxy-L-proline amide”, Tetrahedron: Asymmetry. 2007, 18, 265-270
[55] XU, X. Y.; TANG, Z.; WANG Y. Z.; LUO, S. W.; CUN, L. F.; GONG, L. Z.,“Asymmetric Organocatalytic direct Aldol Reactions of Ketones with Keto Acids and Their Application to the Synthesis of2-Hydroxy-?-butyrolactones”, J. Org. Chem. 2007, 72, 9905-9913
[56] RAJ, M.; VIUMAYA.; GINOTRA, S. K.; SINGH, V. K.;“Highly Enantioselective Direct AldolReaction Catalyzed by Organic Molecules”, Org. Lett. 2006. 8. 4097-4099.
[57] GRUTTADAURIA, M.; GIACALONE, F.; MARCULES, A. M.; NOTOA, R.;“Novel Prolinamide-Supported Polystyrene as Highly Stereoselective and Recyclable Organocatalyst for the Aldol Reaction”. Adv. Synth. Catal. 2008, 350, 1397-1405
[58] SCHWAB, R. S.; GALETTO, F. Z.; AZEREDO, J. B.; BRAGA, A. L.; LüDTKE, D. S.; PAIXǎO, M. W.;“Organocatalytic asymmetric aldol reactions mediated by acysteine-derived prolinamide”Tetrahedron Letters. 2008, 49, 5094–5097.
[59] HE, L.; JIANG, J.; TANG, Z.; CUI, X.; MI, A. Q.; JIANG, Y. Z.; GONG, L. Z.“Highly diastereo- and enantioselective direct aldol reactions of cycloketones with aldehydes catalyzed by a trans-4-tert butyldimethylsiloxy-L-proline amide”, Tetrahedron: Asymmetry. 2007, 18, 265-270
[60] TANIMORI, S.; NAKA, T.; KIRIHATA, M.“Synthesis of a new proline-derived organic catalyst and its evaluation for direct aldol reaction”, Synth. Commun. 2004, 34, 4043-4048
[61] CHEN, J. R.; LU, H. H.; LI, X. Y.; CHENG, L.; WAN, J.; XIAO, W. J.“Readily tunable and bifunctional L-prolinamide derivatives: design and application in the direct enantioselective aldol reactions”, Org. Lett. 2005, 7, 4543-4545
[62] SAMANTA, S.; LIU, J.; DOODA, R.; ZHAO, C. G.“C2-Symmetric bisprolin -amide as a highly efficient catalyst for direct aldol reaction”, Org. Lett. 2005, 7, 5321-5323
[63] CHENG, C. L.; SUN, J., WANG, C.; ZHANG, Y.; WEI, S. Y.; JIANG, F.; WU, Y. D.“Protonated N’-benzyl-N’-prolyl proline hydrazide as highly enantioselective catalyst for direct asymmetric aldol reaction”, Chem. Commun. 2006,2, 215-217
[64] CHEN, J. R.; LI, X. Y.; XING, X. N.; XIAO, W. J.“Sterically and electronically tunable and bifunctional organocatalysts: design and application in asymmetric aldol reaction of cyclic ketones with aldehydes”, J. Org. Chem. 2006, 71, 8198-8202
[65] FU, Y Q.; LI, Z.C., DING, L.N.; TAO, J.C.; ZHANG S.-H.; TANG, M.-S.“Direct asymmetric aldol reaction catalyzed by simple prolinamide phenols”, Tetrahedron: Asymmetry. 2006, 17, 3351-3357
[66]丁一,张雅文,刘艳华,罗晓清,马济美,沈宗旋.“N-[(S)-脯氨酰]羟胺的合成及催化直接不对称羟醛反应研究”,有机化学, 2005, 5, 567-569
[67] JIANG M., ZHU, S. F.; YANG, Y.; GONG, L. Z.; ZHOU, X. G.; ZHOU, Q. L.“Asymmetric aldol reactions catalyzed by new spiro diamine derivatives“, Tetrahedron: Asymmetry. 2006, 17, 384
[68] GUILLENA, G.; HITA, M. C.; NáJERA, C.“BINAM-prolinamides as recoverable catalysts in the direct aldol condensation”, Tetrahedron: Asymmetry. 2006, 17, 729-733
[69] GUILLENA, G.; HITA, M. C.; NáJERA, C.“Organocatalyzed direct aldol condensation using L-proline and BINAM-prolinamides: regio-, diastereo-, and enantioselective controlled synthesis of 1,2-diols”, Tetrahedron: Asymmetry. 2006, 17, 1027-1031
[70] GRYKO, D.; KOWALCZYK, B.; ZAWADZKI, ?.“Bisprolinediamides with the binaphthyl backbone as organocatalysts for the direct asymmetric aldol reaction”, Synlett. 2006, 1059-1062
[71] GUIZZETTI, S.; BENAGLIA, M.; PIGNATARO, L.; PUGLISI, A.“A multifunctional proline- based organic catalyst for enantioselective aldol reaction”, Tetrahedron: Asymmetry 2006, 17, 2754-2760
[72] GRYKO, D.; LIPI?SKI, R.“Asymmetric direct aldol reaction catalysed by L-prolinethioamides”, Eur. J. Org. Chem. 2007, 3864-3876
[73] GRYKO, D.; LIPI?SKI, R.“L-Prolinethioamides-efficient organocatalysts for the direct asymmetric aldol reaction”, Adv. Synth. Catal. 2005, 347, 1948-1952
[74] GRYKO, D.; ZIMNICKA, M.; LIPI?SKI, R.“Br?nsted acids as additives for the direct asymmetric aldol reaction catalyzed by L-prolinethioamides. direct evidence for enamine-iminium catalysis”, J. Org. Chem. 2007, 72, 964-970
[75] BERKESSEL, A.; KOCH, B.; LEX, J.“Proline-derived N-sulfonylcarboxamides: readily available, highly enantioselective and versatile catalysts for direct aldol reactions”, Adv. Synth. Catal. 2004, 346, 1141-1146
[76] COBB, A. J. A.; SHAW, D. M.; LONGBOTTOM, D. A.; LEY, S. V.“Organocatalysis with proline derivatives: improved catalysts for the asymmetric Mannich, nitro-Michael and aldol reactions”, Org. Biomol. Chem. 2005, 3, 84-96
[77] WU, Y. Y.; ZHANG,Y. Z.; YU, M.L.; ZHAO, G.; WANG, S.W.“Highly efficient and reusable dendritic catalysts derived from N-prolylsulfonamide for the asymmetric direct aldol reaction in water”, Org. Lett, 2006, 8, 4417-4420
[78] WANG, W.; MEI, Y.-J.; LI, H.; WANG, J.“A novel pyrrolidine imide catalyzed direct formation ofα,β-unsaturated ketones from unmodified ketones and aldehydes”, Org. Lett, 2005, 7, 601-604
[79] YANG, H.; CARTER, R. G.“N-(p-Dodecylphenylsulfonyl) -2-pyrrolidinecarb oxa -mide:A Practical Proline Mimetic for FacilitatingEnantioselective Aldol Reactions”. Org. Lett., 2008, 10, 4649-4652.
[80] GANDHI, S.; SINGH, V. K.“Synthesis of Chiral Organocatalysts derived from Aziridines: Application in Asymmetric Aldol Reaction”, J. Org. Chem., 2008, 73, 9411-9416.
[81] HARTIKKA, A.; ARVIDSSON, P. I.“Rational design of asymmetric organocatalysts increased reactivity and solvent scope with a tetrazolic acid”, Tetrahedron: Asymmetry 2004, 15, 1831-1834
[82] HARTIKKA, A.; ARVIDSSON, P. I.“5-(Pyrrolidin-2-yl)tetrazole: rationale for the increased reactivity of the tetrazole analogue of proline in organocatalyzed aldol reactions”, Eur. J. Org. Chem. 2005, 4287-4294
[83] ALEXANDER, J. A. C.; DEBORAH A. L.; DAVID M. S.; STEVEN V. L.“5-Pyrrolidin-2-yltetrazole as an asymmetric organocatalyst for the addition of ketones to nitro-olefins”, Chem. Commun. 2004, 1808-1809
[84] TORII, H.; NAKADAI, M.; ISHIHARA, K.; SAITO, S.; YAMAMOTO, H.“Asymmetric Direct Aldol Reaction Assisted by Water and a Proline-Derived Tetrazole Catalyst”, Angew. Chem., Int. Ed. 2004, 43, 1983-1986
[85] LACOSTE, E.; LANDAIS, Y.; SCHENK, K.; VERLHAC, J. B.; VINCENT, J. M.“Benzoimidazole-pyrrolidine (BIP), a highly reactive chiral organocatalyst for aldol process”, Tetrahedron Lett. 2004, 45, 8035-8038
[86] LACOSTE, E.; VAIQUE, E.; BERLANDE, M.; PIANET, I.; VINCENT, J. M.; LANDAIS, Y.“Benzoimidazole-pyrrolidine/H+ (BIP/H+), a highly reactive organocatalyst for asymmetric process”, Eur. J. Org. Chem. 2007, 167-177
[87] DICKERSON, T. J.; JANDA, K. D.“Aqueous Aldol Catalysis by a Nicotine Metabolite”, J. Am. Chem. Soc. 2002, 124, 3220-3221
[88] DICKERSON, T. J.; LOVRLL, T.; MEIJLER, M. M.; NOODLEMAN, L.; JANDA, K. D.“Nornicotine Aqueous Aldol Reactions: Synthetic and Theoretical Investigations into the Origins of Catalysis”, J. Org. Chem. 2004, 69, 6603-6609
[89] ZHENG, J. F.; LI, Y. X.; ZHANG, S. Q., YANG, S. T.; WANG, X. M.; WANG, Y. Z.; BAI, J.; LIU, F. A.“New N-terminal prolyl-dipeptide derivatives as organocatalysts”, Tetrahedron Letters, 2006 ,47 , 793-796.
[90] MASE, N.; NAKAI, Y.; OHARA, N.; YODA, H.; TAKABE, K.; TANAKA, F.; BARBAS, C. F., III.“Organocatalytic direct asymmetric aldol reactions in water”, J. Am. Chem. Soc. 2005, 124, 734-735
[91] MARTIN, H. J.; LIST, B.“Mining sequence space for asymmetric aminocatalysis: N-terminal prolyl-peptides efficiently catalyze enantioselective aldol and michael reactions”, Synlett. 2003, 1901-1902
[92] TANG, Z.; YANG, Z.H.; CUN, L. F.; GONG, L.Z.; MI, A.Q.; JIANG, Y. Z.“Small peptides catalyze highly enantioselective direct aldol reactions of aldehydes with hydroxyacetone: unprecedented regiocontrol in aqueous media”, Org. Lett. 2004, 6, 2285-2287
[93] KOFOED, J.; NIELSEN, J.; REYMOND, J. L.“Discovery of new peptide-based catalysts for the direct asymmetric aldol reaction”, Bioorg. Med. Chem. Lett. 2003, 13, 2445-2447
[94] TSOGOEVA, S. B.; WEI, S. W.“(S)-Histidine-based dipeptides as organic catalysts for direct asymmetric aldol reactions”, Tetrahedron: Asymmetry. 2005, 16, 1947-1951
[95] AKAGAWA, K.; SAKAMOTO, S.; KUDO, K.“Direct asymmetric aldol reaction in aqueous media using polymer-supported peptide”, Tetrahedron Lett. 2005, 46, 8185-8187
[96] KRATTIGER, P.; KOVASY, R.; REVELL, J. D.; IVAN, S.; WENNEMERS, H.“Increased structural complexity leads to higher activity: peptides as efficient and versatile catalysts for asymmetric aldol reactions”, Org. Lett. 2005, 7,1101-1103
[97] SHI, L. X.; SUN, Q.; GE, Z. M.; ZHU, Y. Q.; CHENG, T. M.; LI, R. T.“Dipeptide-catalyzed direct asymmetric aldol reaction”, Synlett. 2004, 2215-2217
[98] ANDREAE, M. R. M.; DAVIS, A. P.“Heterogeneous catalysis of the asymmetric aldol reaction by solid-supported proline-terminated peptides”, Tetrahedron: Asymmetry. 2005, 16, 2487-2492
[99] TSOGOEVA, S. B.; JAGTAP, S. B.; ARDEMASOVA, Z. A.“4-trans-Amino-proline based di- and tetrapeptides as organic catalysts for asymmetric C-C bond formation reactions”, Tetrahedron: Asymmetry. 2006, 17, 989-992
[100] ZOU, W.B.; IBRAHE, I.; DZIEDZIC, P.; SUNDEN, H.; CORDOVA, A.“Small peptides as modular catalysts for the direct asymmetric aldol reaction: ancient peptides with aldolase enzyme activity”, Chem. Commun. 2005, 4946-4948
[101] CORDOVA, A.; ZOU, W. B.; DZIEDZIC, P.; IBRAHEM, I.; REYES, E.; XU, Y. M.“Direct asymmetric intermolecular aldol reactions catalyzed by amino acids and small peptides”, Chem. Eur. J. 2006, 12, 5383-5397
[102] LUPPI, G.; COZZI, P. G.; MONARI, M.; KAPTEIN, B.; BROXTERMAN, Q. B.; TOMASINI, C.,“Dipeptide-Catalyzed Asymmetric Aldol Condensation of Acetone with (N-Alkylated) Isatins”, J. Org. Chem. 2005, 70, 7418-7421
[103] SHEN Z.X.; CHEN, W. H.; JIANG, H.; DING, Y.; LUO, X. Q.; ZHANG, Y. W.“Direct asymmetric aldol reactions catalyzed by (4R)-4-(b-naphtha lenyl) methoxy-(S)-proline”, Chirality. 2005, 17, 119-120
[104] SHEN Z. X.; MA, J. M.; LIU, Y. H.; JIAO, C. J.; LI, M.; ZHANG, Y. W.“β-Cyclodextrin-Immobilized(4S)-Phenoxy-(S)-proline as a Catalyst for Direct. Asymmetric Aldol Reactions”, Chirality. 2005, 17, 556-558
[105] FONT, D.; JIMENO, C.; PERICáS, M. A.“Polystyrene-supported Hydroxyproline: An Insoluble, Recyclable Organocatalyst for the Asymmetric Aldol Reaction in Water”, Org. Lett. 2006, 8, 4653-4655
[106] BELLIS, E.; KOKOTOS, G..“4-Substituted proline as organocatalysts for aldol reactions”, Tetrahedron. 2005, 61, 8669-8676
[107]BELLIS, E.; VASILATOU, K.; KOKOTOS, G.“4-Substituted prolyl sulfonamides as enantioselective organocatalysts for aldol reactions”, Synthesis. 2005, 2407-2411
[108]HAYASHI, Y. J.; ARATAKE, S.; OKANO, T.; TAKAHASHI, J.; SUMIYA, T.; SHOJI, M.“Combined proline–surfactant organocatalyst for the highly diastereo- and enantioselective aqueous direct cross-aldol reaction of aldehydes”, Angew. Chem., Int. Ed. 2006, 45, 5527-5529
[109] BENAGAIA, M.; CELENTANO, G.; COZZIA, F.“Enantioselective aldol condensations catalyzed by poly(ethylene glycol)-supported praline”, Adv. Synth. Catal. 2001, 343, 171-173
[110] MIAO, W. S.; CHAN, T. H.“Ionic-liquid-supported organocatalyst:efficient and recyclable ionic-liquid-anchored proline for asymmetric aldol reaction”, Adv. Synth. Catal. 2006, 348, 1711-1718
[111] LIU, Y. X.; SUN, Y. N., TAN, H. H.; TAO, J. C.“Asymmetric Aldol Reaction Catalyzed by New Recyclable Polystyrene-supported L-proline in the Presence of Water”, Catal Lett, 2008 , 120 , 281-287.
[112] GU, L. Q.; YU, M. L.; WU, X. Y.; ZHANG, Y. Z.; ZHAO, G.“4,4’-Disu bstituted L-prolines as highly enantioselective catalysts for direct aldol reactions”, Adv. Synth. Catal. 2006, 348, 2223-2228
[113] LIMBACH, M.“β-Homoamino acids as catalysts in enantioselective intra and intermolecular aldol reactions”, Tetrahedron Lett. 2006. 47. 3843-3847
[114] DAVIES, S. G.; SHEPPARD, RUTH, L.; SMITH, A. D.; THOMSON, J. E.“Highly enantio-selective organocatalysis of the Hajos–Parrish–Eder–Sauer– Wiechert reaction by theβ-amino acid cispentacin”, Chem. Commun. 2005, 3802-3804
[115] TANG, X. P.; LIéGAULT, B.; RENAUD, J. L.; BRUNEAU, C.“(S, S, S)- Perhy droindolic acid: efficient catalyst for direct asymmetric aldol reactionfrom aromatic aldehydes”, Tetrahedron: Asymmetry. 2006, 17, 2187-2190
[116] KANO, T.; TAKAI, J.; TOKUDA, O.;MARUOKA, K.“Design of an Axially Chiral Amino Acid with a Binaphthyl Backbone as an Organocatalyst for a Direct Asymmetric Aldol Reaction”, Angew. Chem. Int. Ed. 2005, 44, 3055-3057
[117] KANO, T.; TOKUDA, O.; MARUOKA, K.“Synthesis of a biphenyl-based axially chiral amino acid as a highly efficient catalyst for the direct asymmetric aldol reaction”, Tetrahedron Lett. 2006, 47, 7423-7426
[118] KANO, T.; TOKUDA, O.; TAKAI, J.; MARUOKA, K.“Design of a binaphthyl-based axially chiral amino acid as an organocatalyst for direct asymmetric aldol reactions”, Chem. Asian. J. 2006, 1–2, 210-215
[119] GU, Q.; WANG, X. F.; WANG, L.; WU, X.Y.; ZHOU, Q. L.“(2S, 5S)-Pyrrolidine-2, 5-dicarboxylic acid, an efficient chiral organocatalyst for direct aldol reaction”, Tetrahedron: Asymmetry. 2006, 17, 1537-1540
[120] DINéR, P.; AMEDJKOUH, M.“Aminophosphonates as organocatalysts in the direct asymmetric aldol reaction: towards syn selectivity in the presence of Lewis bases”, Org. Biomol. Chem. 2006, 4, 2091-2096
[121] CORDOVA, A.; NOTZ, W.; BARBAS, C. F., III.“Direct organocatalytic aldol reaction in buffered aqueous media”, Chem. Commun. 2002, 3024-3025
[122] PENG, Y. Y.; DING, Q. P.; LI, Z. C.; WANG, P. G.; CHENG, J.P.“Proline catalyzed aldol reaction in aqueous micelles: an environmentally friendly reaction system”, Tetrahedron Lett. 2003, 44, 3871-3875
[123] CODOVA, A.; ZOU, W.B.; IBRAHEM, I.; REYES, E.; ENGQVIST, M.; LIAO, W.W.“Acyclic amino acid-catalyzed direct asymmetric aldol reactions: alanine, the simplest stereoselective organocatalyst”, Chem. Commun. 2005, 3586-3588
[124] JIANG, Z.Q.; LIANG, Z.; WU, X.Y.; LU, Y. X.“Asymmetric aldol reaction catalyzed by tryptophan in water”, Chem. Commun. 2006, 2801-2803
[125] CHIMMI S. S.; MAHAJAN, D.; BABU, V. V. S.“Protonated chiral prolinamide catalyzed enantioselective direct aldol reaction in water”, Tetrahedron Lett.2005, 46, 5617-5619
[126] CHIMMI, S. S.; MAHAJAN, D.“Small organic molecule catalyzed enantioseletive direct aldol reaction in water”, Tetrahedron: Asymmetry. 2006, 17, 2108-2119
[127] HAYASHI, Y.; SUMIYA, T.; TAKAHASHI, J.; GOTOH, H.; URUSHIMA, T.; SHOJI, M.“Highly diastereo- and enantioselective direct aldol reactions in water”, Angew. Chem. Int. Ed. 2006, 45, 958-961
[128] PERLMUTTER, P.“Conjugate addition reactions in organic synhtesis“. Pergamon, Oxford. 1992.
[129] ROSSITER, B, E.; SWINGLE, N. M. Chem. Rev. 1992, 92, 771-806
[130] BERNER, O. M.; TEDESCHI, L.; ENDERS, D.“Asymmetric Michael Additions to Nitroalkenes”, Eur. J. Org. Chem. 2002, 1877-1894
[131] LIST, B.; POJARLIEV, P.; MARTIN, H. J.“Efficient proline-catalyzed michael additions of unmodified ketones to nitro olefins”, Org. Lett. 2001, 3, 2423-2425
[132] SAKTHIVEL, K.; NOTZ, W.; BUI, T.; BARBAS, C. F., III.“Amino Acid Catalyzed Direct Asymmetric Aldol Reactions: A Bioorganic Approach to Catalytic Asymmetric Carbon-Carbon Bond-Forming Reactions”J. Am. Chem. Soc. 2001, 123, 5260-5267
[133] RASALKAR, M. S.; POTDAR, M. K.; MOHILE, S. S.; SALUNKHE, M. M.“An ionic iquid influenced l-proline catalysed asymmetric Michael addition of ketones to nitrostyrene”. J. Mol. Catal. A 2005, 235, 267-270
[134] TERAKADO, D.; TAKANO, M.; ORIYAMA, T.“Highly Enantioselective (S)-Homoproline-catalyzed Michael Addition Reactions of Ketones toβ-Nitrostyrenes”, Chemistry Lett. 2005, 34, 962-963
[135] ZHU, M.K.; CUN, L. F.; MI, A.Q.; JIANG, Y.Z.; GONG, L.Z.“A highly enantioselective organocatalyst for the Michael addition of cyclic ketones to nitroolefins”, Tetrahedron: Asymmetry. 2006, 17, 491-493
[136] MASE, N.; WATANABER, KAORI.; YODA, H.; TAKABE, K.; TANAKA, F.; BARBAS, C. F. III.“Organocatalytic Direct Michael Reaction of Ketones andAldehydes withβ-Nitrostyrene in Brine”, J. Am. Chem. Soc. 2006, 128, 4966-4967
[137] PANSARE, S. V.; PANDYA, K.“Simple diamine- and triamine-protonic acid catalysts for the enantioselective michael addition of cyclic ketones to nitroalkenes”, J. Am. Chem. Soc. 2006, 128, 9624-9625
[138] VISHNUMAYA.; SINGH, V. K.“Highly enantioselective water-compatible organocatalyst for michael reaction of ketones to nitroolefins”, Org. Lett. 2007, 9, 1117-1119
[139] ANDREY, O.; ALEXAKIS, A.; TOMASSINI, A.; BERNARDINELLI, G.“The use of n-alkyl-2,2’-bipyrrolidine derivatives as organocatalysts for the asymmetric michael addition of ketones and aldehydes to nitroolefins”, Adv. Synth. Catal. 2004, 346, 1147-1168
[140] COBB, A. J. A.; LONGBOTTOM, D. A.; SHAW, D. M.; LEY, S. V.“5-Pyrrolidin-2-yltetrazole as an asymmetric organocatalyst for the addition of ketones to nitro-olefins”, Chem. Commun. 2004, 1808-1809
[141] MITCHELL, C. E. T.; COBB, A. J. A.; LEY, S. V.“A homo-proline tetrazole as an improved organocatalyst for the asymmetric michael addition of carbonyl compounds to nitro-olefins”, Synlett. 2005, 611-614
[142] WANG, W.; WANG, J.; LI, H.“Direct, highly enantioselective pyrrolidine sulfonamide catalyzed michael addition of aldehydes to nitrostyrenes”, Angew. Chem. Int. Ed. 2005, 44, 1369-1371
[143] ZU, L. S.; WANG, J.; LI, H.; WANG, W.“A recyclable fluorous (S)-pyrrolidine sulfonamide promoted direct, highly enantioselective michael addition of ketones and aldehydes to nitroolefins in water”, Org. Lett. 2006, 8, 3077-3079
[144] ISHII,T.; FUJIOKA, S.; SEKIGUCHI, Y.; KOTSUKI, H.“A new class of chiral pyrrolidine-pyridine conjugate base catalysts for use in asymmetric michael addition reactions”, J. Am. Chem. Soc. 2004, 126, 9558-9559
[145] LUO, S. Z.; XU, H.; MI, X. L.; LI, J. Y.; ZHENG, X. X.; CHENG, J. P.“Evolution of Pyrrolidine-Type Asymmetric Organocatalysts by“Click”Chemistry”, J. Org. Chem. 2006, 71, 9244-9247
[146] LUO, S. Z.; MI, X. L.; LIU, S.; XU, H.; CHENG, J. P.“Surfactant-type asymmetric organocatalyst: organocatalytic asymmetric Michael addition to nitrostyrenes in water”, Chem. Commun. 2006, 3687-3689
[147] ALMASI, D.; ALONSO, D. A.; NáJERA, C.“Enantioselective conjugate addition of ketones toβ-nitrostyrenes catalyzed by 1,2-amino alcohol-derived prolinamides”, Tetrahedron: Asymmetry. 2006, 17, 2064-2068
[148]PALOMO, C.; VERA, S.; MIELGO, A.; BENGOA, E. G.“Highly efficient asymmetric michael addition of aldehydes to nitroalkenes catalyzed by a simple trans-4-hydroxyprolylamide”, Angew. Chem. Int. Ed. 2006, 45, 5984-5987
[149] ALMASüI, D.; ALONSO, D. A.; NA′JERA, C.“Enantioselective conjugate addition of ketones toβ-nitrostyrenes catalyzed by 1,2-amino alcohol-derived prolinamides”Tetrahedron: Asymmetry 2006,17, 2064-2068
[150] CLARKE, M. L.; FUENTES, J. A.“Self- assembly of organocatalysts: fine-tuning organocatalytic reactions”, Angew. Chem. Int. Ed. 2007, 46, 930-933
[151] YALALOV, D. A.; TSOGOEVA, S. B.; SCHMATA, S.“Chiral Thiourea-Based Bifunctional Organocatalysts in theAsymmetric Nitro-Michael Addition: A Joint Experimental-Theoretical Study”AdV. Synth. Catal. 2006, 348, 826-832
[152] TSOGOEVA, S. B.; SHENG, W. W.,“Highly enantioselective addition of ketones to nitroolefins catalyzed by new thiourea–amine bifunctional organocatalysts”Chem. Commun. 2006, 1451-1453
[153] HUANG, H.; JACOBSEN, E. N.“Highly Enantioselective Direct Conjugate Addition of Ketones to Nitroalkenes Promoted by A Chiral Primary Amine-Thiourea Catalyst”. J. Am. Chem. Soc. 2006, 128, 7170-1771.
[154] CAO, C. L.; YE, M. C.; SUN, X. L.; TANG, Y.“Pyrrolidine-thiourea as a bifunctional organocatalyst: highly enantioselective michael addition of cyclohexanone to nitroolefins”, Org. Lett. 2006, 8, 2901-2904
[155] CAO, Y. J.; LAI, Y. Y.; WANG, X.; LI, Y. J.; XIAO, W. J.“Michael additions inwater of ketones to nitroolefins catalyzed by readily tunable and bifunctional pyrrolidine–thiourea organocatalysts”, Tetrahedron Lett. 2007, 48, 21-24
[156] LIU, K.; CUI, H. F.; NIE, J.; DONG, K.Y.; LI, X. J.; MA, J. A.“Highly Enantioselective michael addition of aromatic ketones to nitroolefins promoted by chiral bifunctional primary amine-thiourea catalysts based on saccharides”, Org. Lett. 2007, 9, 923-925
[157] MCCOEY, S. H.; CONNON, S. J.“Readily accessible 9-epi-amino cinchona alkaloid derivatives promote efficient, highly enantioselective additions of aldehydes and ketones to nitroolefins”, Org. Lett. 2007, 9, 599-602
[158] BENAGLIA, M.; CELENTANO, G.; COZZI, F.“Enantioselective Aldol Condensations Catalyzed by Poly(ethylene glycol)-Supported Proline”, Adv. Synth. Catal. 2001, 343, 171–173;
[159] BENAGLIA, M.; CINQUINI, M.; COZZI, F.; PUGLISIS, A.; CELENTANO, G.“Poly(Ethylene Glycol)-Supported Proline: AVersatile Catalyst for the Enantioselective Aldol and Iminoaldol Reactions”Adv. Synth.Catal. 2002, 344, 533–542.
[160] SALVADORI, P.; PINI, D.; PETRI, A. Synlett 1999, 1181–1190;
[161] SALUZZO, C.; HALLE, R.; TOUCHARD, F.; FACHE, F.; SCHULZ, E.; LEMAIRE, M. J.Organomet. Chem. 2000, 603, 30–39;
[162] CALDERO′N, F.; FERNA′NDEZ, R.; SANCHEZ, F.; MAYORALAS, A. F.“Asymmetric Aldol Reaction Using Immobilized Proline on Mesoporous Support”, Adv. Synth. Catal. 2005, 347, 1395–1403
[163] DOYAGU¨EZ, E. G.; CALDERO′N, F.; MAYORALAS, A. F.,“Asymmetric Aldol Reaction Catalyzed by a Heterogenized Proline on a Mesoporous Support. The Role of the Nature of Solvents”J. Org. Chem. 2007, 72,9353-9356.
[164] YAN, J.; WANG, L.,“Asymmetric Aldol Reactions Catalyzed by Efficient and Recyclable Silica-Supported Proline-Based Peptides”CHIRALITY, 2009, 21 413-420.
[165] OCHIAI E. Recent Japanese work on the chemistry of pyridine 1-oxide andrelated compounds [ J ]. J. Org. Chem, 1953, 18:534-551
[166]王志样,张志炳. 4-氨基吡啶合成的改进[J].中国医药工业杂志, 2001, 32 (2) : 83- 84.
[167]杨春常,范平,黄治清,等.对氨基吡啶的合成与研究[J].辽宁化工, 1991, 28 (3) : 36237.
[168] CHEN, F.B, SHI HUANG, H. Z., LIU, F.Y, PENG Y.G.,“Proline-based dipeptides with two amide units as organocatalyst for theasymmetric aldol reaction of cyclohexanone with aldehydes”. Tetrahedron 64, 2008, 17, 9585-9591.