有机催化不对称Michael加成反应在手性吲哚-3-酮衍生物合成中的应用
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摘要
本论文主要包括两部分内容：
1.对近几年有机催化Michael加成反应的研究进展进行了综述
Michael加成反应是有机化学合成反应中构建碳-碳键的重要反应之一,一直是化学工作者感兴趣的研究课题。在过去的几年里,不对称有机催化Michael加成反应得到了迅速发展,成为不对称催化研究领域的一个热点。和其他有机催化反应一样,它具有条件温和、反应时间短、立体选择性好、原料及反应后处理简单等优点。随着各种催化体系的发展和完善,有机催化Michael加成反应已经成为合成众多重要的药物中间体和天然产物手性合成子的有效手段。本章主要总结了有机催化Michael加成反应在近几年的研究进展。
2.有机催化不对称Michael加成反应合成手性吲哚-3-酮衍生物的研究
吲哚-3-酮衍生物广泛存在于许多天然产物和药物分子中,同时也是很多重要生物活性分子合成的起始原料。我们用简单的乙酰基保护的吲哚-3-酮分别与硝基烯烃,不饱和醛和不饱和酮酯进行加成反应,在相应的有机小分子催化剂的催化下,均以很好的产率和立体选择性合成了手性的2-位取代的吲哚酮类化合物,该产物可以转化为手性的2-位取代吲哚和吲哚啉并环戊烷类化合物。该反应简洁高效,催化效率高,为手性的氧化吲哚及吲哚类化合物的合成提供了一种切实有效的方法。
This thesis is composed of two parts:
1. The review of asymmetric organocatalytic Michael addition
The Michael addition reaction is one of the most important reactions for the formation of carbon-carbon bonds in organic synthesis, which has attracted considerable interest from chemists all over the world. Remarkable progress has been made in this field in recent years and the research in organocatalytic asymmetric Michael addition has become a big hit in the field of asymmetric catalysis. It has the advantages of mild reaction conditions, short reaction time, excellent stereoselectivities, readily available starting materials with a minimum of manual operations. The organocatalytic asymmetric Michael addition has become effective methods for the synthesis of many important drug intermediates and chiral synthons of natural products. This chapter reviews the recent development of asymmetric organocatalytic Michael addition reaction according to the catalyst system used.
2. Organocatalytic asymmetric Michael addition for the synthesis of chiral indolin-3-one derivatives
2-Substituted indolin-3-ones exist widely in many natural products and pharmaceutical compounds, and have been used as versatile intermediates for the synthesis of biologically active organic compounds and natural-products. We investigated the reactions of1-acetylindolin-3-ones with nitroolefins, α,β-unsaturated aldehydes and β,γ-unsaturated α-keto esters catalyzed by corresponding organocatalysts,2-substituted indolin-3-ones were obtained in good yields and stereoslectivities, which could be transformed to chiral2-substituted indoles and cyclopentyl[b]indoline compounds. This concise and simple reaction with high catalytic efficiency could be an effective method for the synthesis of chiral3-oxindoles and indole compounds.
1.对近几年有机催化Michael加成反应的研究进展进行了综述
Michael加成反应是有机化学合成反应中构建碳-碳键的重要反应之一,一直是化学工作者感兴趣的研究课题。在过去的几年里,不对称有机催化Michael加成反应得到了迅速发展,成为不对称催化研究领域的一个热点。和其他有机催化反应一样,它具有条件温和、反应时间短、立体选择性好、原料及反应后处理简单等优点。随着各种催化体系的发展和完善,有机催化Michael加成反应已经成为合成众多重要的药物中间体和天然产物手性合成子的有效手段。本章主要总结了有机催化Michael加成反应在近几年的研究进展。
2.有机催化不对称Michael加成反应合成手性吲哚-3-酮衍生物的研究
吲哚-3-酮衍生物广泛存在于许多天然产物和药物分子中,同时也是很多重要生物活性分子合成的起始原料。我们用简单的乙酰基保护的吲哚-3-酮分别与硝基烯烃,不饱和醛和不饱和酮酯进行加成反应,在相应的有机小分子催化剂的催化下,均以很好的产率和立体选择性合成了手性的2-位取代的吲哚酮类化合物,该产物可以转化为手性的2-位取代吲哚和吲哚啉并环戊烷类化合物。该反应简洁高效,催化效率高,为手性的氧化吲哚及吲哚类化合物的合成提供了一种切实有效的方法。
This thesis is composed of two parts:
1. The review of asymmetric organocatalytic Michael addition
The Michael addition reaction is one of the most important reactions for the formation of carbon-carbon bonds in organic synthesis, which has attracted considerable interest from chemists all over the world. Remarkable progress has been made in this field in recent years and the research in organocatalytic asymmetric Michael addition has become a big hit in the field of asymmetric catalysis. It has the advantages of mild reaction conditions, short reaction time, excellent stereoselectivities, readily available starting materials with a minimum of manual operations. The organocatalytic asymmetric Michael addition has become effective methods for the synthesis of many important drug intermediates and chiral synthons of natural products. This chapter reviews the recent development of asymmetric organocatalytic Michael addition reaction according to the catalyst system used.
2. Organocatalytic asymmetric Michael addition for the synthesis of chiral indolin-3-one derivatives
2-Substituted indolin-3-ones exist widely in many natural products and pharmaceutical compounds, and have been used as versatile intermediates for the synthesis of biologically active organic compounds and natural-products. We investigated the reactions of1-acetylindolin-3-ones with nitroolefins, α,β-unsaturated aldehydes and β,γ-unsaturated α-keto esters catalyzed by corresponding organocatalysts,2-substituted indolin-3-ones were obtained in good yields and stereoslectivities, which could be transformed to chiral2-substituted indoles and cyclopentyl[b]indoline compounds. This concise and simple reaction with high catalytic efficiency could be an effective method for the synthesis of chiral3-oxindoles and indole compounds.
引文
[1]Michael, A. J. Prakt. Chem.1886,35,349.
[2]List, B., Lerner, R. A., Barbas, C. F. Ⅲ. Proline-catalyzed Direct Asymmetric Aldol Reactions. J. Am. Chem. Soc.2000,122,2395-2396.
[3]Hanessian, S. and Pham, V. Catalytic Asymmetric Conjugate Addition of Nitroalkanes to Cycloalkenones. Org. Lett.2000,2,2975-2978.
[4]List, B.; Pojarliev, P.; and Martin, H. J. Efficient Proline-catalyzed Michael Additions of Unmodified Ketones to Nitro Olefins. Org. Lett.2001,3,2423-2425.
[5]Enders, D.; Seki, A. Proline-Catalyzed Enantioselective Michael Additions of Ketones to Nitrostyrene. Synlett 2002,26-28.
[6]Betancort, J. M. and Barbas, C. F. Ⅲ. Catalytic Direct Asymmetric Michael Reactions: Taming Naked Aldehyde Donors. Org. Lett.2001,3,3737-3740.
[7]Alexakis, A. and Andrey, O. Diamine-Catalyzed Asymmetric Michael Additions of Aldehydes and Ketones to Nitrostyrene. Org. Lett.2002,4,3611-3614.
[8]Mase, N.; Thayumanavan, R.; Tanaka, F. and Barbas, C. F. Ⅲ. Direct Asymmetric Organocatalytic Michael Reactions of a,a-Disubstituted Aldehydes with β-Nitrostyrenes for the Synthesis of Quaternary Carbon-Containing Products. Org. Lett.2004,6,2527-2530.
[9]Ishii, T.; Fujioka, S.; Sekiguchi, Y. and 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.
[10]Knudsen, K. R.; Mitchell, C. E. T. and Ley, S. V. Asymmetric Organocatalytic Conjugate Addition of Malonates to Enones Using a Proline Tetrazole Catalyst. Chem. Commun.2006, 66-68.
[11]Wang, W.; Wang, J. and Li H. Direct, Highly Enantioselective Pyrrolidine Sulfonamide Catalyzed Michael Addition of Aldehydes to Nitrostyrenes. Angew. Chem., Int. Ed.2005,44, 1369-1371.
[12]Wang, J.; Li, H.; Zu, L.-S.; Wang W. Highly Enantioselective Organocatalytic Michael Addition Reactions of Ketones with Chalcones. Adv. Synth. Catal.2006,348,425-428.
[13]Luo, S.; Mi, X.; 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.
[14]Hayashi, Y.; Gotoh, H.; Hayashi, T. and Shoji, M. Diphenylprolinol Silyl Ethers as Efficient Organocatalysts for the Asymmetric Michael Reaction of Aldehydes and Nitroalkenes. Angew. Chem., Int. Ed.2005,44,4212-4215.
[15]Chi, Y.-G. and Gellman, S. H. Diphenylprolinol Methyl Ether:(?) A Highly Enantioselective Catalyst for Michael Addition of Aldehydes to Simple Enones. Org. Lett.2005,7, 4253-4256.
[16]Brandau, S.; Landa, A.; Franzen, J.; Marigo, M. and Jogensen, K. A. Organocatalytic Conjugate Addition of Malonates to α,β-Unsaturated Aldehydes:Asymmetric Formal Synthesis of (-)-Paroxetine, Chiral Lactams, and Lactones. Angew. Chem., Int. Ed.2006,45, 4305-4309.
[17]Ma, A.-Q.; Zhu, S.-L. and Ma, D.-W. Enantioselective Organocatalytic Michael Addition of Malonates to α,β-Unsaturated Aldehydes in Water. Tetrahedron Lett.2008,49,3075-3077.
[18]Bertelsen, S.; Diner, P.; Johansen, R. L.; Jorgensen, K. A. Asymmetric Organocatalytic β-Hydroxylation of α,β-Unsaturated Aldehydes. J. Am. Chem. Soc.2007,129,1536-1537.
[19]Wu, J.-B.; Ni, B.-K. and Headley, A. D. Di(methylimidazole)prolinol Silyl Ether Catalyzed Highly Michael Addition of Aldehydes to Nitroolefins in Water. Org. Lett.2009,11, 3354-3356.
[20]Zheng, Z.-L.; Perkins, B. L.; and Ni, B. Diarylprolinol Silyl Ether Salts as New, Efficient, Water-Soluble, and Recyclable Organocatalysts for the Asymmetric Michael Addition on Water. J. Am. Chem. Soc.2010,132,50-51.
[21]Tan, B.; Zeng, X.-F.; Lu, Y.-P.; Chua, P. J. and Zhong, G.-F. Rational Design of Organocatalyst:Highly Stereoselective Michael Addition of Cyclic Ketones to Nitroolefins. Org. Lett.,2009,11,1927-1930.
[22]Quintard, A.; Lefranc, A. and Alexakis, A. Highly Enantioselective Direct Vinylogous Michael Addition of γ-Butenolide to Enals. Org. Lett.,2011,13,1540-1543.
[23]Ban, S.-R.; Xie, H.-Y.; Zhu, X.-X.; and Li, Q.-S. Highly Enantioselective Michael Addition of Ketones to Nitroolefins with a Pyrrolidine-Based Phthalimide as an Enamine-Type Organocatalyst. Eur. J. Org. Chem.2011,6413-6417.
[24]Chen, J.-R.; Fu, L.; Zou, Y.-Q.; Chang, N.-J.; Rong, J. and Xiao, W.-J. Pyrrolidinyl-sulfamide Derivatives as a New Class of Bifunctional Organocatalysts for Direct Asymmetric Michael Addition of Cyclohexanone to Nitroalkenes. Org. Biomol. Chem.2011, 9,5280-5287.
[25]Paras, N. A. and MacMillan, D. W. C. New Strategies in Organic Catalysis:The First Enantioselective Organocatalytic Friedel-Crafts Alkylation. J. Am. Chem. Soc.2001,123, 4370-4371.
[26]Brown, S. P.; Goodwin, N. C. and MacMillan, D. W. C. The First Enantioselective Organocatalytic Mukaiyama-Michael Reaction:A Direct Method for the Synthesis of Enantioenriched y-Butenolide Architecture. J. Am. Chem. Soc.2002,124,1172-1173.
[27]Brown S. P., Goodwin N. C., MacMillan, D. W. C. The First Enantioselective Organocatalytic Mukaiyama-Michael Reaction:A Direct Method for the Synthesis of Enantioenriched δ-Butenolide Architecture. J. Am. Chem. Soc.2003,125,1192-1194.
[28]Fonseca, M. T. H. and List, B. Catalytic Asymmetric Intramolecular Michael Reaction of Aldehydes. Angew. Chem., Int. Ed.2004,43,3958-3960.
[29]Halland, N.; Hazell, R. G. and J(?)rgensen, K. A. Organocatalytic Asymmetric Conjugate Addition of Nitroalkanes to α,β-Unsaturated Enones Using Novel Imidazoline Catalysts. J. Org. Chem.2002,67,8331-8338.
[30]Halland, N.; Aburel, P. S. and J(?)rgensen, K. A. Highly Enantioselective Organocatalytic Conjugate Addition of Malonates to Acyclic α,β-Unsaturated Enones. Angew. Chem., Int. Ed. 2003,42,661-665.
[31]Sigman, M. S.; Jacobsen, E. N. Schiff Base Catalysts for the Asymmetric Strecker Reaction Identified and Optimized from Parallel Synthetic Libraries. J. Am. Chem. Soc.1998,720, 4901-4902.
[32]Okiho, T.; Hoashi, Y.; Takemoto, Y. Enantioselective Michael Reaction of Malonates to Nitroolefins Catalyzed by Bifunctional Organocatalysts. J. Am. Chem. Soc.2003,125, 12672-12673.
[33]Hoashi, Y.; Okino, T. and Takemoto, Y. Enantioselective Michael Addition to α,β-Unsaturated Imides Catalyzed by a Bifunctional Organocatalyst. Angew. Chem., Int. Ed. 2005,44,4032-4035.
[34]Okino, T.; Hoashi, Y.; Furukawa, T.; Xu, X.; Takemoto, Y. Enantio-and Diastereoselective Michael Reaction of 1,3-Dicarbonyl Compounds to Nitroolefins Catalyzed by a Bifunctional Thiourea. J. Am. Chem. Soc.2005,127,119-125.
[35]Vakulya, B.; Varga, S.; Csampai, A.; Soos, T. Highly Enantioselective Conjugate Addition of Nitromethane to Chalcones Using Bifunctional Cinchona Organocatalysts. Org. Lett.2005,7, 1967-1969.
[36]McCooey, S. H.; Connon, S. J. Urea- and Thiourea-Substituted Cinchona Alkaloid Derivatives as Highly Efficient Bifunctional Organocatalysts for the Asymmetric Addition of Malonate to Nitroalkenes:Inversion of Configuration at C9 Dramatically Improves Catalyst Performance. Angew. Chem., Int. Ed.2005,44,6367-6370.
[37]Ye, J.; Dixon, D. J.; Hynes, P. S. Enantioselective Organocatalytic Michael Addition of Malonate Esters to Nitro Olefins Using Bifunctional Cinchonine Derivatives. Chem. Commun.2005,4481-4483.
[38]Wang, J.; Li, H.; Zu, L.; Wang, W. Chiral Binaphthyl-Derived Amine-Thiourea Organocatalyst-Promoted Asymmetric Morita-Baylis-Hillman Reaction. Org. Lett.2005,7, 4293-4296.
[39]Tsogoeva, S. B.; Yalalov, D. A.; Hateley, M. J.; Weckbecker, C.; Huthmacher, K. Asymmetric Organocatalysis with Novel Chiral Thiourea Derivatives:Bifunctional Catalysts for the Strecker and Nitro-Michael Reactions. Eur. J. Org. Chem.2005,23,4995-5000.
[40]Yalalov, D. A.; Tsogoeva, S. B.; Schmatz, S. Chiral Thiourea-Based Bifunctional Organocatalysts in the Asymmetric Nitro-Michael Addition:A Joint Experimental-Theoretical Study. Adv. Synth. Catal.2006,348,826-832.
[41]Tsogoeva, S. B.; Wei, S. W. Highly Enantioselective Addition of Ketones to Nitroolefins Catalyzed by New Thiourea-amine Bifunctional Organocatalysts. Chem. Commun.2006, 1451-1453.
[42]Huang, H.-B. and Jacobsen, E. N. Highly Enantioselective Direct Conjugate Addition of Ketones to Nitroalkenes Promoted by A Chiral Primary Amine-Thiourea Catalyst. J. Am. Chem. Soc.2006,128,7170-7171.
[43]Cao, C.-L.; Ye, M.-C.; Sun, X.-L. and Tang, Y. Pyrrolidine-Thiourea as a Bifunctional Organocatalyst:(?) Highly Enantioselective Michael Addition of Cyclohexanone to Nitroolefins. Org. Lett.2006,8,2901-2904.
[44]Sibi, M. P. and Itoh, K. Organocatalysis in Conjugate Amine Additions. Synthesis of β-Amino Acid Derivatives. J. Am. Chem. Soc.2007,12,8064-8065.
[45]Peng, F.-Z.; Shao, Z.-H.; Fan, B.-M.; Song, H.; Li, G.-P. and Zhang, H.-B. Organocatalytic Enantioselective Michael Addition of 2,4-Pentandione to Nitroalkenes Promoted by Bifunctional Thioureas with Central and Axial Chiral Elements. J. Org. Chem.2008,73, 5202-5205.
[46]Li, P.-F.; Wen, S.-G.; Yu, F.; Liu, Q.-X.; Li, W.-J.; Wang, Y.-C.; Liang, X.-M. and Ye, J.-X. Enantioselective Organocatalytic Michael Addition of Malonates to α,β-Unsaturated Ketones. Org. Lett.2009,11,753-756.
[47]Dong, X.-Q.; Teng, H.-L. and Wang, C.-J. Highly Enantioselective Direct Michael Addition of Nitroalkanes to Nitroalkenes Catalyzed by Amine-Thiourea Bearing Multiple Hydrogen-Bonding Donors. Org. Lett.2009,11,1265-1268.
[48]Lu, H.-H.; Zhang, F.-G.; Meng, X.-G.; Duan, S.-W. and Xiao, W.-J. Enantioselective Michael Reactions of β,β-Disubstituted Nitroalkenes:A New Approach to β2,2-Amino Acids with Hetero-Quaternary Stereocenters. Org. Lett.2009,11,3946-3949.
[49]Wu, C.-L.; Li, W.-J.; Yang, J.-J.; Liang, X.-M. and Ye, J.-X. Asymmetric Organocatalytic Michael Addition of Anthrone to Enone. Org. Biomol. Chem.2010,8,3244-3250.
[50]Liao, Y.-H.; Liu, X.-L.; Wu, Z.-J.; Cun, L.-F.; Zhang, X.-M. and Yuan, W.-C. Highly Diastereo- and Enantioselective Michael Additions of 3-Substituted Oxindoles to Maleimides Catalyzed by Chiral Bifunctional Thiourea-Tertiary Amine. Org. Lett.2010,12,2896-2899.
[51]Li, H.-M.; Wang, Y.; Tang, L. and Deng, L. Highly Enantioselective Conjugate Addition of Malonate and β-Ketoester to Nitroalkenes:(?) Asymmetric C-C Bond Formation with New Bifunctional Organic Catalysts Based on Cinchona Alkaloids. J. Am. Chem. Soc.2004,126, 9906-9907.
[52]Xie, J.-W.; Chen, W.; Li, R.; Zeng, M.; Du, W.; Yue, L.; Chen, Y.-C.; Wu, Y.; Zhu, J.; and Deng, J.-G. Highly Asymmetric Michael Addition to α,β-Unsaturated Ketones Catalyzed by 9-Amino-9-deoxyepiquinine. Angew. Chem., Int. Ed.2007,46,389-392.
[53]Liu, X.-L.; Wu, Z.-J.; Du, X.-L.; Zhang, X.-M. and Yuan, W.-C. Amino-Indanol-Catalyzed Asymmetric Michael Additions of Oxindoles to Protected 2-Amino-l-nitroethenes for the Synthesis of 3,3'-Disubstituted Oxindoles Bearing α,β-Diamino Functionality. J. Org. Chem. 2011,76,4008-4017.
[54]Ooi, T.; Takada, S.; Fujioka, S. and Maruoka, K. N-Spiro Chiral Quaternary Ammonium Bromide Catalyzed Diastereo- and Enantioselective Conjugate Addition of Nitroalkanes to Cyclic α,β-Unsaturated Ketones under Phase-Transfer Conditions. Org. Lett.2005,7, 5143-5146.
[55]He, R.-J.; Ding, C.; Maruoka, K. Phosphonium Salts as Chiral Phase-transfer Catalysts: Asymmetric Michael and Mannich reactions of 3-aryloxindoles. Angew. Chem., Int. Ed.2009, 48,4559-4561.
[56]He, R.-J.; Shirakawa, S. and Maruoka, K. Enantioselective Base-Free Phase-Transfer Reaction in Water-Rich Solvent. J. Am. Chem. Soc.2009,131,16620-16621.
[57]Horstmann, T. E.; Guerin, D. J. and Miller, S. J. Asymmetric Conjugate Addition of Azide to α,β-Unsaturated Carbonyl Compounds Catalyzed by Simple Peptides. Angew. Chem., Int. Ed. 2000,39,3635-3638
[58]Xu, Y.-M. and Cordova, A. Simple Highly Modular Acyclic Amine-catalyzed Direct Enantioselective Addition of Ketones to Nitro-olefins. Chem. Commun.,2006,460-462.
[59]Xu, Y.-M.; Zou, W.-B.; Sunde'n, H.; Ibrahem, I.; Co'rdova, A.; Small Peptide-Catalyzed Enantioselective Addition of Ketones to Nitroolefins. Adv. Synth. Catal.2006,348,418-424.
[1]Bui, T.; Syed, S. and Barbas, C. F. III. Thiourea-Catalyzed Highly Enantio- and Diastereoselective Additions of Oxindoles to Nitroolefins:Application to the Formal Synthesis of (+)-Physostigmine. J. Am. Chem. Soc.2009,131,8758-8759.
[2]For some related organocatalyzed reactions involving 2-oxindoles as nucleophiles, see:(a) Liu, X.-L.; Liao, Y.-H.; Wu, Z.-J.; Cun, L.-F.; Yuan, W.-C. Organocatalytic Enantioselective Hydroxymethylation of Oxindoles with Paraformaldehyde as C1 Unit. J. Org. Chem.2010,75, 4872-4875. (b) He, R.; Ding, C.; Maruoka, K. Phosphonium Salts as Chiral Phase-transfer Catalysts:Asymmetric Michael and Mannich Reactions of 3-Aryloxindoles. Angew. Chem., Int. Ed.2009,48,4559-4561. (c) Chen, X.-H.; Wei, Q.; Luo, S.-W.; Xiao, H.; Gong, L.-Z. Organocatalytic Synthesis of Spiro[pyrrolidin-3,3'-oxindoles] with High Enantiopurity and Structural Diversity. J. Am. Chem. Soc.2009,131,13819-13825. (d) Galzerano, P.; Bencivenni, G.; Pesciaioli, F.; Mazzanti, A.; Giannichi, B.; Sambri, L.; Bartoli, G.; Melchiorre, P. Asymmetric Iminium Ion Catalysis with a Novel Bifunctional Primary Amine Thiourea: Controlling Adjacent Quaternary and Tertiary Stereocenters. Chem.-Eur. J.2009,15, 7846-7849. (e) Duffey, T. A.; Shaw, S. A.; Vedejs, E. AcOLeDMAP and BnOLeDMAP: Conformationally Restricted Nucleophilic Catalysts for Enantioselective Rearrangement of Indolyl Acetates and Carbonates.J. Am. Chem. Soc.2009,131,14-15. (f) Cheng, L.; Liu, L.; Wang, D.; Chen, Y.-J. Highly Enantioselective and Organocatalytic a-Amination of 2-Oxindoles. Org. Lett.2009,11,3874-3877. (g) Jiang, K.; Peng, J.; Cui, H.-L.; Chen, Y.-C. Organocatalytic Asymmetric Allylic Alkylation of Oxindoles with Morita-Baylis-Hillman Carbonates. Chem. Commun.2009,26,3955-3957. (h) Cheng, L.; Liu, L.; Jia, H.; Wang, D.; Chen, Y.-J. Enantioselective Organocatalytic anti-Mannich-Type Reaction of N-Unprotected 3-Substituted 2-Oxindoles with Aromatic N-Ts-aldimines. J. Org. Chem.2009,74,4650-4653. (i) Bui, T.; Borregan, M.; Barbas, C. F. Expanding the Scope of Cinchona Alkaloid-Catalyzed Enantioselective a-Aminations of Oxindoles:A Versatile Approach to Optically Active 3-Amino-2-oxindole Derivatives. J. Org. Chem.2009,74,8935-8938.
[3]Kazuhiro, H.; Kouhei, M.; Tamami, K.; Masahiro, H.; Masanori, S.; Tomomi, K. Asymmetric Alkylation of 2-Monosubstituted Indolin-3-ones. Heterocycles 2007,73,641-650.
[4]For recent reviews of bifunctional amine-thiourea mediated catalysis, see:(a) Tian, S.; Chen, Y.; Hang, J.; Tang, L.; McDaid, P.; Deng, L. Asymmetric Organic Catalysis with Modified Cinchona Alkaloids. Acc. Chem. Res.2004,37,621-631. (b) Takemoto, Y. Recognition and Activation by Ureas and Thioureas:Stereoselective Reactions Using Ureas and Thioureas as Hydrogen-bonding Donors. Org. Biomol. Chem.2005,3,4299-4306. (c) Connon, S. J. Organocatalysis Mediated by (Thio)urea Derivatives. Chem.-Eur. J.2006,12,5418-5427. (d) Doyle, A. G.; Jacobsen, E. N. Small-Molecule H-Bond Donors in Asymmetric Catalysis. Chem. Rev.2007,107,5713-5743. (e) Connon, S. J. Asymmetric Catalysis with Bifunctional Cinchona Alkaloid-based Urea and Thiourea Organocatalysts. Chem. Commun.2008, 2499-2510.
[5]For some selected examples, see:(a) Tomomi, K.; Atsuyo, O.;Yasuyuki, T.; Masanori, S. Enantioselective Total Synthesis of (-)-Pseudophrynaminol Through Tandem Olefination, Isomerization and Asymmetric Claisen Rearrangement. Tetrahedron Lett. 2003, 44, 1591-1593. (b) Guyen, B.; Schultes, C. M.; Haze,l P.; Mann, J.; Neidle, S. Synthesis and Evaluation of Analogues of 10H-indolo[3,2-b]quinoline as G-quadruplex Stabilising Ligands and Potential Inhibitors of the Enzyme Telomerase. Org. Biomol. Chem. 2004, 2, 981-988. (c) Tomomi, K.; Masashi, S.; Mayu, O.; Atsuyo, O.; Romi, T.; Masanori S. Total Synthesis of (±)-Flustramines A and C, (±)-Flustramide A, and (-)- and (+)-Debromoflustramines A. J. Org. Chem. 2008, 73, 5959-5964. (d) Satoshi, T.; Toshimasa, I.; Yuh-suke, K.; Kohta, M.; Naoko, B.; Kazuhiro, H.; Tomomi, K. Total Syntheses of (-)-Fructigenine A and (-)-5-N-Acetylardeemin. J. Org. Chem. 2010, 75, 1126-1131.
[6]Selected successful examples: (a) Taylor, M.S.; Jacobsen, E. N. Highly Enantioselective Catalytic Acyl-Pictet-Spengler Reactions. J. Am. Chem. Soc. 2004, 126, 10558-10559. (b) Seayad, J.; Seayad, A. M.; List, B. Catalytic Asymmetric Pictet-Spengler Reaction. J. Am. Chem. Soc. 2006, 128, 1086-1087. (c) Raheem, I. T.; Thiara, P. S.; Peterson, E. A.; Jacobsen, E. N. Enantioselective Pictet-Spengler-Type Cyclizations of Hydroxylactams:(?) H-Bond Donor Catalysis by Anion Binding. J. Am. Chem. Soc. 2007, 129, 13404-13405. (d) Lee, S.; MacMillan, D. W. C. Organocatalytic Vinyl and Friedel-Crafts Alkylations with Trifluoroborate Salts. J. Am. Chem.Soc. 2007,129, 15438-15439.
[7]For selected examples of amino catalysis, see: (a) Marigo, M.; Wabnitz, T. C; Fielenbach, D.; J(?)rgensen, K. A. Enantioselective Organocatalyzed a Sulfenylation of Aldehydes. Angew. Chem., Int. Ed. 2005, 44, 794-797. (b) Hayashi, Y.; Gotoh, H.; Hayashi, T.; Shoji, M. Diphenylprolinol Silyl Ethers as Efficient Organocatalysts for the Asymmetric Michael Reaction of Aldehydes and Nitroalkenes. Angew. Chem., Int. Ed. 2005, 44, 4212-4215. (c) Marigo, M.; Franzen, J.; Poulsen, T. B.; Zhuang, W.; J0rgensen, K. A. Asymmetric Organocatalytic Epoxidation of α,β-Unsaturated Aldehydes with Hydrogen Peroxide. J. Am. Chem. Soc. 2005, 127, 6964-6965. (d) Wang, W.; Li, H.; Wang, J.; Zu, L. Enantioselective Organocatalytic Tandem Michael-Aldol Reactions: D One-Pot Synthesis of Chiral Thiochromenes. J. Am. Chem. Soc. 2006,128, 10354-10355. (e) Chi, Y.; Guo, L.; Kopf, N. A.; Gellman, S. H. Enantioselective Organocatalytic Michael Addition of Aldehydes to Nitroethylene: Efficient Access to γ2-Amino Acids. J. Am. Chem. Soc. 2008, 130, 5608-5609. (f) Garci'a-Garci'a, P.; Lade'pe che, A.; Haider, R.; List, B. Catalytic Asymmetric Michael Reactions of Acetaldehyde. Angew. Chem., Int. Ed. 2008, 47, 4719-4721.
[8]For selected examples of asymmetric conjugate reaction of β,γ-unsaturated α-keto esters see: (a) Zhou, L.; Lin, L.-L.; Wang, W.-T. ; Ji, J.; Liu, X.-H.; Feng, X.-M. Highly Enantioselective Michael Addition of Malonates to β,γ-Unsaturated α-Ketoesters Catalyzed by Chiral N,N'-Dioxide-Yttrium(III) Complexes with Convenient Procedure. Chem. Commun. 2010, 46, 3601-3603. (b) Zhao, S.-L.; Zheng, C.-W.; Wang, H.-F.; Zhao, G Highly Enantioselective Michael Addition of a-Substituted Cyano Ketones to β,γ-Unsaturated a-Keto Esters using Bifunctional Thiourea-Tertiary Amine Catalysts: An Easy Access to Chiral Dihydropyrans. Adv. Synth. Catal. 2009, 357, 2811-2816. (c) Herrera, R. P.; Monge, D.; M-Zamora, E.; Ferna'ndez, R.; Lassaletta, J. M. Organocatalytic Conjugate Addition of Formaldehyde N,N-Dialkylhydrazones to β,γ-Unsaturated a-Keto Esters. Org. Lett. 2007,11, 3303-3306. (d) Gao, Y.-J.; Ren, Q.; Wang, L.; Wang, J. Enantioselective Synthesis of Coumarins Catalyzed by a Bifunctional Amine-Thiourea Catalyst. Chem.-Eur. J.2010,16,13068-13071. (e) Xu, D.-Q.; Wang, Y.-F.; Wang, W.; Luo, S.-P.; Xia, A.-B.; Xu, Z.-Y. Chiral Squaramides as Highly Enantioselective Catalysts for Michael Addition Reactions of 4-Hydroxycoumarins and 4-Hydroxypyrone to β,γ-Unsaturated a-Keto Esters. Chem.-Eur. J.2010,16,4177-4179.
[9]Rueping, M.; Nachtsheim, B.; Moreth, S. A.; Bolte, M. Asymmetric Bronsted Acid Catalysis: Enantioselective Nucleophilic Substitutions and 1,4-Additions. Angew. Chem., Int. Ed.2008, 47,593-596.
[2]List, B., Lerner, R. A., Barbas, C. F. Ⅲ. Proline-catalyzed Direct Asymmetric Aldol Reactions. J. Am. Chem. Soc.2000,122,2395-2396.
[3]Hanessian, S. and Pham, V. Catalytic Asymmetric Conjugate Addition of Nitroalkanes to Cycloalkenones. Org. Lett.2000,2,2975-2978.
[4]List, B.; Pojarliev, P.; and Martin, H. J. Efficient Proline-catalyzed Michael Additions of Unmodified Ketones to Nitro Olefins. Org. Lett.2001,3,2423-2425.
[5]Enders, D.; Seki, A. Proline-Catalyzed Enantioselective Michael Additions of Ketones to Nitrostyrene. Synlett 2002,26-28.
[6]Betancort, J. M. and Barbas, C. F. Ⅲ. Catalytic Direct Asymmetric Michael Reactions: Taming Naked Aldehyde Donors. Org. Lett.2001,3,3737-3740.
[7]Alexakis, A. and Andrey, O. Diamine-Catalyzed Asymmetric Michael Additions of Aldehydes and Ketones to Nitrostyrene. Org. Lett.2002,4,3611-3614.
[8]Mase, N.; Thayumanavan, R.; Tanaka, F. and Barbas, C. F. Ⅲ. Direct Asymmetric Organocatalytic Michael Reactions of a,a-Disubstituted Aldehydes with β-Nitrostyrenes for the Synthesis of Quaternary Carbon-Containing Products. Org. Lett.2004,6,2527-2530.
[9]Ishii, T.; Fujioka, S.; Sekiguchi, Y. and 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.
[10]Knudsen, K. R.; Mitchell, C. E. T. and Ley, S. V. Asymmetric Organocatalytic Conjugate Addition of Malonates to Enones Using a Proline Tetrazole Catalyst. Chem. Commun.2006, 66-68.
[11]Wang, W.; Wang, J. and Li H. Direct, Highly Enantioselective Pyrrolidine Sulfonamide Catalyzed Michael Addition of Aldehydes to Nitrostyrenes. Angew. Chem., Int. Ed.2005,44, 1369-1371.
[12]Wang, J.; Li, H.; Zu, L.-S.; Wang W. Highly Enantioselective Organocatalytic Michael Addition Reactions of Ketones with Chalcones. Adv. Synth. Catal.2006,348,425-428.
[13]Luo, S.; Mi, X.; 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.
[14]Hayashi, Y.; Gotoh, H.; Hayashi, T. and Shoji, M. Diphenylprolinol Silyl Ethers as Efficient Organocatalysts for the Asymmetric Michael Reaction of Aldehydes and Nitroalkenes. Angew. Chem., Int. Ed.2005,44,4212-4215.
[15]Chi, Y.-G. and Gellman, S. H. Diphenylprolinol Methyl Ether:(?) A Highly Enantioselective Catalyst for Michael Addition of Aldehydes to Simple Enones. Org. Lett.2005,7, 4253-4256.
[16]Brandau, S.; Landa, A.; Franzen, J.; Marigo, M. and Jogensen, K. A. Organocatalytic Conjugate Addition of Malonates to α,β-Unsaturated Aldehydes:Asymmetric Formal Synthesis of (-)-Paroxetine, Chiral Lactams, and Lactones. Angew. Chem., Int. Ed.2006,45, 4305-4309.
[17]Ma, A.-Q.; Zhu, S.-L. and Ma, D.-W. Enantioselective Organocatalytic Michael Addition of Malonates to α,β-Unsaturated Aldehydes in Water. Tetrahedron Lett.2008,49,3075-3077.
[18]Bertelsen, S.; Diner, P.; Johansen, R. L.; Jorgensen, K. A. Asymmetric Organocatalytic β-Hydroxylation of α,β-Unsaturated Aldehydes. J. Am. Chem. Soc.2007,129,1536-1537.
[19]Wu, J.-B.; Ni, B.-K. and Headley, A. D. Di(methylimidazole)prolinol Silyl Ether Catalyzed Highly Michael Addition of Aldehydes to Nitroolefins in Water. Org. Lett.2009,11, 3354-3356.
[20]Zheng, Z.-L.; Perkins, B. L.; and Ni, B. Diarylprolinol Silyl Ether Salts as New, Efficient, Water-Soluble, and Recyclable Organocatalysts for the Asymmetric Michael Addition on Water. J. Am. Chem. Soc.2010,132,50-51.
[21]Tan, B.; Zeng, X.-F.; Lu, Y.-P.; Chua, P. J. and Zhong, G.-F. Rational Design of Organocatalyst:Highly Stereoselective Michael Addition of Cyclic Ketones to Nitroolefins. Org. Lett.,2009,11,1927-1930.
[22]Quintard, A.; Lefranc, A. and Alexakis, A. Highly Enantioselective Direct Vinylogous Michael Addition of γ-Butenolide to Enals. Org. Lett.,2011,13,1540-1543.
[23]Ban, S.-R.; Xie, H.-Y.; Zhu, X.-X.; and Li, Q.-S. Highly Enantioselective Michael Addition of Ketones to Nitroolefins with a Pyrrolidine-Based Phthalimide as an Enamine-Type Organocatalyst. Eur. J. Org. Chem.2011,6413-6417.
[24]Chen, J.-R.; Fu, L.; Zou, Y.-Q.; Chang, N.-J.; Rong, J. and Xiao, W.-J. Pyrrolidinyl-sulfamide Derivatives as a New Class of Bifunctional Organocatalysts for Direct Asymmetric Michael Addition of Cyclohexanone to Nitroalkenes. Org. Biomol. Chem.2011, 9,5280-5287.
[25]Paras, N. A. and MacMillan, D. W. C. New Strategies in Organic Catalysis:The First Enantioselective Organocatalytic Friedel-Crafts Alkylation. J. Am. Chem. Soc.2001,123, 4370-4371.
[26]Brown, S. P.; Goodwin, N. C. and MacMillan, D. W. C. The First Enantioselective Organocatalytic Mukaiyama-Michael Reaction:A Direct Method for the Synthesis of Enantioenriched y-Butenolide Architecture. J. Am. Chem. Soc.2002,124,1172-1173.
[27]Brown S. P., Goodwin N. C., MacMillan, D. W. C. The First Enantioselective Organocatalytic Mukaiyama-Michael Reaction:A Direct Method for the Synthesis of Enantioenriched δ-Butenolide Architecture. J. Am. Chem. Soc.2003,125,1192-1194.
[28]Fonseca, M. T. H. and List, B. Catalytic Asymmetric Intramolecular Michael Reaction of Aldehydes. Angew. Chem., Int. Ed.2004,43,3958-3960.
[29]Halland, N.; Hazell, R. G. and J(?)rgensen, K. A. Organocatalytic Asymmetric Conjugate Addition of Nitroalkanes to α,β-Unsaturated Enones Using Novel Imidazoline Catalysts. J. Org. Chem.2002,67,8331-8338.
[30]Halland, N.; Aburel, P. S. and J(?)rgensen, K. A. Highly Enantioselective Organocatalytic Conjugate Addition of Malonates to Acyclic α,β-Unsaturated Enones. Angew. Chem., Int. Ed. 2003,42,661-665.
[31]Sigman, M. S.; Jacobsen, E. N. Schiff Base Catalysts for the Asymmetric Strecker Reaction Identified and Optimized from Parallel Synthetic Libraries. J. Am. Chem. Soc.1998,720, 4901-4902.
[32]Okiho, T.; Hoashi, Y.; Takemoto, Y. Enantioselective Michael Reaction of Malonates to Nitroolefins Catalyzed by Bifunctional Organocatalysts. J. Am. Chem. Soc.2003,125, 12672-12673.
[33]Hoashi, Y.; Okino, T. and Takemoto, Y. Enantioselective Michael Addition to α,β-Unsaturated Imides Catalyzed by a Bifunctional Organocatalyst. Angew. Chem., Int. Ed. 2005,44,4032-4035.
[34]Okino, T.; Hoashi, Y.; Furukawa, T.; Xu, X.; Takemoto, Y. Enantio-and Diastereoselective Michael Reaction of 1,3-Dicarbonyl Compounds to Nitroolefins Catalyzed by a Bifunctional Thiourea. J. Am. Chem. Soc.2005,127,119-125.
[35]Vakulya, B.; Varga, S.; Csampai, A.; Soos, T. Highly Enantioselective Conjugate Addition of Nitromethane to Chalcones Using Bifunctional Cinchona Organocatalysts. Org. Lett.2005,7, 1967-1969.
[36]McCooey, S. H.; Connon, S. J. Urea- and Thiourea-Substituted Cinchona Alkaloid Derivatives as Highly Efficient Bifunctional Organocatalysts for the Asymmetric Addition of Malonate to Nitroalkenes:Inversion of Configuration at C9 Dramatically Improves Catalyst Performance. Angew. Chem., Int. Ed.2005,44,6367-6370.
[37]Ye, J.; Dixon, D. J.; Hynes, P. S. Enantioselective Organocatalytic Michael Addition of Malonate Esters to Nitro Olefins Using Bifunctional Cinchonine Derivatives. Chem. Commun.2005,4481-4483.
[38]Wang, J.; Li, H.; Zu, L.; Wang, W. Chiral Binaphthyl-Derived Amine-Thiourea Organocatalyst-Promoted Asymmetric Morita-Baylis-Hillman Reaction. Org. Lett.2005,7, 4293-4296.
[39]Tsogoeva, S. B.; Yalalov, D. A.; Hateley, M. J.; Weckbecker, C.; Huthmacher, K. Asymmetric Organocatalysis with Novel Chiral Thiourea Derivatives:Bifunctional Catalysts for the Strecker and Nitro-Michael Reactions. Eur. J. Org. Chem.2005,23,4995-5000.
[40]Yalalov, D. A.; Tsogoeva, S. B.; Schmatz, S. Chiral Thiourea-Based Bifunctional Organocatalysts in the Asymmetric Nitro-Michael Addition:A Joint Experimental-Theoretical Study. Adv. Synth. Catal.2006,348,826-832.
[41]Tsogoeva, S. B.; Wei, S. W. Highly Enantioselective Addition of Ketones to Nitroolefins Catalyzed by New Thiourea-amine Bifunctional Organocatalysts. Chem. Commun.2006, 1451-1453.
[42]Huang, H.-B. and Jacobsen, E. N. Highly Enantioselective Direct Conjugate Addition of Ketones to Nitroalkenes Promoted by A Chiral Primary Amine-Thiourea Catalyst. J. Am. Chem. Soc.2006,128,7170-7171.
[43]Cao, C.-L.; Ye, M.-C.; Sun, X.-L. and Tang, Y. Pyrrolidine-Thiourea as a Bifunctional Organocatalyst:(?) Highly Enantioselective Michael Addition of Cyclohexanone to Nitroolefins. Org. Lett.2006,8,2901-2904.
[44]Sibi, M. P. and Itoh, K. Organocatalysis in Conjugate Amine Additions. Synthesis of β-Amino Acid Derivatives. J. Am. Chem. Soc.2007,12,8064-8065.
[45]Peng, F.-Z.; Shao, Z.-H.; Fan, B.-M.; Song, H.; Li, G.-P. and Zhang, H.-B. Organocatalytic Enantioselective Michael Addition of 2,4-Pentandione to Nitroalkenes Promoted by Bifunctional Thioureas with Central and Axial Chiral Elements. J. Org. Chem.2008,73, 5202-5205.
[46]Li, P.-F.; Wen, S.-G.; Yu, F.; Liu, Q.-X.; Li, W.-J.; Wang, Y.-C.; Liang, X.-M. and Ye, J.-X. Enantioselective Organocatalytic Michael Addition of Malonates to α,β-Unsaturated Ketones. Org. Lett.2009,11,753-756.
[47]Dong, X.-Q.; Teng, H.-L. and Wang, C.-J. Highly Enantioselective Direct Michael Addition of Nitroalkanes to Nitroalkenes Catalyzed by Amine-Thiourea Bearing Multiple Hydrogen-Bonding Donors. Org. Lett.2009,11,1265-1268.
[48]Lu, H.-H.; Zhang, F.-G.; Meng, X.-G.; Duan, S.-W. and Xiao, W.-J. Enantioselective Michael Reactions of β,β-Disubstituted Nitroalkenes:A New Approach to β2,2-Amino Acids with Hetero-Quaternary Stereocenters. Org. Lett.2009,11,3946-3949.
[49]Wu, C.-L.; Li, W.-J.; Yang, J.-J.; Liang, X.-M. and Ye, J.-X. Asymmetric Organocatalytic Michael Addition of Anthrone to Enone. Org. Biomol. Chem.2010,8,3244-3250.
[50]Liao, Y.-H.; Liu, X.-L.; Wu, Z.-J.; Cun, L.-F.; Zhang, X.-M. and Yuan, W.-C. Highly Diastereo- and Enantioselective Michael Additions of 3-Substituted Oxindoles to Maleimides Catalyzed by Chiral Bifunctional Thiourea-Tertiary Amine. Org. Lett.2010,12,2896-2899.
[51]Li, H.-M.; Wang, Y.; Tang, L. and Deng, L. Highly Enantioselective Conjugate Addition of Malonate and β-Ketoester to Nitroalkenes:(?) Asymmetric C-C Bond Formation with New Bifunctional Organic Catalysts Based on Cinchona Alkaloids. J. Am. Chem. Soc.2004,126, 9906-9907.
[52]Xie, J.-W.; Chen, W.; Li, R.; Zeng, M.; Du, W.; Yue, L.; Chen, Y.-C.; Wu, Y.; Zhu, J.; and Deng, J.-G. Highly Asymmetric Michael Addition to α,β-Unsaturated Ketones Catalyzed by 9-Amino-9-deoxyepiquinine. Angew. Chem., Int. Ed.2007,46,389-392.
[53]Liu, X.-L.; Wu, Z.-J.; Du, X.-L.; Zhang, X.-M. and Yuan, W.-C. Amino-Indanol-Catalyzed Asymmetric Michael Additions of Oxindoles to Protected 2-Amino-l-nitroethenes for the Synthesis of 3,3'-Disubstituted Oxindoles Bearing α,β-Diamino Functionality. J. Org. Chem. 2011,76,4008-4017.
[54]Ooi, T.; Takada, S.; Fujioka, S. and Maruoka, K. N-Spiro Chiral Quaternary Ammonium Bromide Catalyzed Diastereo- and Enantioselective Conjugate Addition of Nitroalkanes to Cyclic α,β-Unsaturated Ketones under Phase-Transfer Conditions. Org. Lett.2005,7, 5143-5146.
[55]He, R.-J.; Ding, C.; Maruoka, K. Phosphonium Salts as Chiral Phase-transfer Catalysts: Asymmetric Michael and Mannich reactions of 3-aryloxindoles. Angew. Chem., Int. Ed.2009, 48,4559-4561.
[56]He, R.-J.; Shirakawa, S. and Maruoka, K. Enantioselective Base-Free Phase-Transfer Reaction in Water-Rich Solvent. J. Am. Chem. Soc.2009,131,16620-16621.
[57]Horstmann, T. E.; Guerin, D. J. and Miller, S. J. Asymmetric Conjugate Addition of Azide to α,β-Unsaturated Carbonyl Compounds Catalyzed by Simple Peptides. Angew. Chem., Int. Ed. 2000,39,3635-3638
[58]Xu, Y.-M. and Cordova, A. Simple Highly Modular Acyclic Amine-catalyzed Direct Enantioselective Addition of Ketones to Nitro-olefins. Chem. Commun.,2006,460-462.
[59]Xu, Y.-M.; Zou, W.-B.; Sunde'n, H.; Ibrahem, I.; Co'rdova, A.; Small Peptide-Catalyzed Enantioselective Addition of Ketones to Nitroolefins. Adv. Synth. Catal.2006,348,418-424.
[1]Bui, T.; Syed, S. and Barbas, C. F. III. Thiourea-Catalyzed Highly Enantio- and Diastereoselective Additions of Oxindoles to Nitroolefins:Application to the Formal Synthesis of (+)-Physostigmine. J. Am. Chem. Soc.2009,131,8758-8759.
[2]For some related organocatalyzed reactions involving 2-oxindoles as nucleophiles, see:(a) Liu, X.-L.; Liao, Y.-H.; Wu, Z.-J.; Cun, L.-F.; Yuan, W.-C. Organocatalytic Enantioselective Hydroxymethylation of Oxindoles with Paraformaldehyde as C1 Unit. J. Org. Chem.2010,75, 4872-4875. (b) He, R.; Ding, C.; Maruoka, K. Phosphonium Salts as Chiral Phase-transfer Catalysts:Asymmetric Michael and Mannich Reactions of 3-Aryloxindoles. Angew. Chem., Int. Ed.2009,48,4559-4561. (c) Chen, X.-H.; Wei, Q.; Luo, S.-W.; Xiao, H.; Gong, L.-Z. Organocatalytic Synthesis of Spiro[pyrrolidin-3,3'-oxindoles] with High Enantiopurity and Structural Diversity. J. Am. Chem. Soc.2009,131,13819-13825. (d) Galzerano, P.; Bencivenni, G.; Pesciaioli, F.; Mazzanti, A.; Giannichi, B.; Sambri, L.; Bartoli, G.; Melchiorre, P. Asymmetric Iminium Ion Catalysis with a Novel Bifunctional Primary Amine Thiourea: Controlling Adjacent Quaternary and Tertiary Stereocenters. Chem.-Eur. J.2009,15, 7846-7849. (e) Duffey, T. A.; Shaw, S. A.; Vedejs, E. AcOLeDMAP and BnOLeDMAP: Conformationally Restricted Nucleophilic Catalysts for Enantioselective Rearrangement of Indolyl Acetates and Carbonates.J. Am. Chem. Soc.2009,131,14-15. (f) Cheng, L.; Liu, L.; Wang, D.; Chen, Y.-J. Highly Enantioselective and Organocatalytic a-Amination of 2-Oxindoles. Org. Lett.2009,11,3874-3877. (g) Jiang, K.; Peng, J.; Cui, H.-L.; Chen, Y.-C. Organocatalytic Asymmetric Allylic Alkylation of Oxindoles with Morita-Baylis-Hillman Carbonates. Chem. Commun.2009,26,3955-3957. (h) Cheng, L.; Liu, L.; Jia, H.; Wang, D.; Chen, Y.-J. Enantioselective Organocatalytic anti-Mannich-Type Reaction of N-Unprotected 3-Substituted 2-Oxindoles with Aromatic N-Ts-aldimines. J. Org. Chem.2009,74,4650-4653. (i) Bui, T.; Borregan, M.; Barbas, C. F. Expanding the Scope of Cinchona Alkaloid-Catalyzed Enantioselective a-Aminations of Oxindoles:A Versatile Approach to Optically Active 3-Amino-2-oxindole Derivatives. J. Org. Chem.2009,74,8935-8938.
[3]Kazuhiro, H.; Kouhei, M.; Tamami, K.; Masahiro, H.; Masanori, S.; Tomomi, K. Asymmetric Alkylation of 2-Monosubstituted Indolin-3-ones. Heterocycles 2007,73,641-650.
[4]For recent reviews of bifunctional amine-thiourea mediated catalysis, see:(a) Tian, S.; Chen, Y.; Hang, J.; Tang, L.; McDaid, P.; Deng, L. Asymmetric Organic Catalysis with Modified Cinchona Alkaloids. Acc. Chem. Res.2004,37,621-631. (b) Takemoto, Y. Recognition and Activation by Ureas and Thioureas:Stereoselective Reactions Using Ureas and Thioureas as Hydrogen-bonding Donors. Org. Biomol. Chem.2005,3,4299-4306. (c) Connon, S. J. Organocatalysis Mediated by (Thio)urea Derivatives. Chem.-Eur. J.2006,12,5418-5427. (d) Doyle, A. G.; Jacobsen, E. N. Small-Molecule H-Bond Donors in Asymmetric Catalysis. Chem. Rev.2007,107,5713-5743. (e) Connon, S. J. Asymmetric Catalysis with Bifunctional Cinchona Alkaloid-based Urea and Thiourea Organocatalysts. Chem. Commun.2008, 2499-2510.
[5]For some selected examples, see:(a) Tomomi, K.; Atsuyo, O.;Yasuyuki, T.; Masanori, S. Enantioselective Total Synthesis of (-)-Pseudophrynaminol Through Tandem Olefination, Isomerization and Asymmetric Claisen Rearrangement. Tetrahedron Lett. 2003, 44, 1591-1593. (b) Guyen, B.; Schultes, C. M.; Haze,l P.; Mann, J.; Neidle, S. Synthesis and Evaluation of Analogues of 10H-indolo[3,2-b]quinoline as G-quadruplex Stabilising Ligands and Potential Inhibitors of the Enzyme Telomerase. Org. Biomol. Chem. 2004, 2, 981-988. (c) Tomomi, K.; Masashi, S.; Mayu, O.; Atsuyo, O.; Romi, T.; Masanori S. Total Synthesis of (±)-Flustramines A and C, (±)-Flustramide A, and (-)- and (+)-Debromoflustramines A. J. Org. Chem. 2008, 73, 5959-5964. (d) Satoshi, T.; Toshimasa, I.; Yuh-suke, K.; Kohta, M.; Naoko, B.; Kazuhiro, H.; Tomomi, K. Total Syntheses of (-)-Fructigenine A and (-)-5-N-Acetylardeemin. J. Org. Chem. 2010, 75, 1126-1131.
[6]Selected successful examples: (a) Taylor, M.S.; Jacobsen, E. N. Highly Enantioselective Catalytic Acyl-Pictet-Spengler Reactions. J. Am. Chem. Soc. 2004, 126, 10558-10559. (b) Seayad, J.; Seayad, A. M.; List, B. Catalytic Asymmetric Pictet-Spengler Reaction. J. Am. Chem. Soc. 2006, 128, 1086-1087. (c) Raheem, I. T.; Thiara, P. S.; Peterson, E. A.; Jacobsen, E. N. Enantioselective Pictet-Spengler-Type Cyclizations of Hydroxylactams:(?) H-Bond Donor Catalysis by Anion Binding. J. Am. Chem. Soc. 2007, 129, 13404-13405. (d) Lee, S.; MacMillan, D. W. C. Organocatalytic Vinyl and Friedel-Crafts Alkylations with Trifluoroborate Salts. J. Am. Chem.Soc. 2007,129, 15438-15439.
[7]For selected examples of amino catalysis, see: (a) Marigo, M.; Wabnitz, T. C; Fielenbach, D.; J(?)rgensen, K. A. Enantioselective Organocatalyzed a Sulfenylation of Aldehydes. Angew. Chem., Int. Ed. 2005, 44, 794-797. (b) Hayashi, Y.; Gotoh, H.; Hayashi, T.; Shoji, M. Diphenylprolinol Silyl Ethers as Efficient Organocatalysts for the Asymmetric Michael Reaction of Aldehydes and Nitroalkenes. Angew. Chem., Int. Ed. 2005, 44, 4212-4215. (c) Marigo, M.; Franzen, J.; Poulsen, T. B.; Zhuang, W.; J0rgensen, K. A. Asymmetric Organocatalytic Epoxidation of α,β-Unsaturated Aldehydes with Hydrogen Peroxide. J. Am. Chem. Soc. 2005, 127, 6964-6965. (d) Wang, W.; Li, H.; Wang, J.; Zu, L. Enantioselective Organocatalytic Tandem Michael-Aldol Reactions: D One-Pot Synthesis of Chiral Thiochromenes. J. Am. Chem. Soc. 2006,128, 10354-10355. (e) Chi, Y.; Guo, L.; Kopf, N. A.; Gellman, S. H. Enantioselective Organocatalytic Michael Addition of Aldehydes to Nitroethylene: Efficient Access to γ2-Amino Acids. J. Am. Chem. Soc. 2008, 130, 5608-5609. (f) Garci'a-Garci'a, P.; Lade'pe che, A.; Haider, R.; List, B. Catalytic Asymmetric Michael Reactions of Acetaldehyde. Angew. Chem., Int. Ed. 2008, 47, 4719-4721.
[8]For selected examples of asymmetric conjugate reaction of β,γ-unsaturated α-keto esters see: (a) Zhou, L.; Lin, L.-L.; Wang, W.-T. ; Ji, J.; Liu, X.-H.; Feng, X.-M. Highly Enantioselective Michael Addition of Malonates to β,γ-Unsaturated α-Ketoesters Catalyzed by Chiral N,N'-Dioxide-Yttrium(III) Complexes with Convenient Procedure. Chem. Commun. 2010, 46, 3601-3603. (b) Zhao, S.-L.; Zheng, C.-W.; Wang, H.-F.; Zhao, G Highly Enantioselective Michael Addition of a-Substituted Cyano Ketones to β,γ-Unsaturated a-Keto Esters using Bifunctional Thiourea-Tertiary Amine Catalysts: An Easy Access to Chiral Dihydropyrans. Adv. Synth. Catal. 2009, 357, 2811-2816. (c) Herrera, R. P.; Monge, D.; M-Zamora, E.; Ferna'ndez, R.; Lassaletta, J. M. Organocatalytic Conjugate Addition of Formaldehyde N,N-Dialkylhydrazones to β,γ-Unsaturated a-Keto Esters. Org. Lett. 2007,11, 3303-3306. (d) Gao, Y.-J.; Ren, Q.; Wang, L.; Wang, J. Enantioselective Synthesis of Coumarins Catalyzed by a Bifunctional Amine-Thiourea Catalyst. Chem.-Eur. J.2010,16,13068-13071. (e) Xu, D.-Q.; Wang, Y.-F.; Wang, W.; Luo, S.-P.; Xia, A.-B.; Xu, Z.-Y. Chiral Squaramides as Highly Enantioselective Catalysts for Michael Addition Reactions of 4-Hydroxycoumarins and 4-Hydroxypyrone to β,γ-Unsaturated a-Keto Esters. Chem.-Eur. J.2010,16,4177-4179.
[9]Rueping, M.; Nachtsheim, B.; Moreth, S. A.; Bolte, M. Asymmetric Bronsted Acid Catalysis: Enantioselective Nucleophilic Substitutions and 1,4-Additions. Angew. Chem., Int. Ed.2008, 47,593-596.