具有多氢键给体的金鸡纳碱类硫脲催化剂的合成及其催化性能研究
|
摘要
本论文主要研究了具有多氢键给体的金鸡纳碱类硫脲催化剂的设计、合成及其在不对称催化中的应用。以奎宁或奎宁丁为原料,在MsCl, Et3N/NaN3或DPPA/DIAD/PPh3的作用下,将金鸡纳碱中的9-OH通过一步转化得到含有金鸡钠碱骨架的叠氮化合物。该叠氮化合物在三苯基膦和二硫化碳作用下可以很容易地转变成为含有异硫氰基团的金鸡纳碱,进而可以与一系列的氨基醇或单酰基(磺酰基)保护的二胺反应以较高的产率得到含有多个氢键给体的多官能硫脲催化剂。
为了考察该类催化剂在不对称合成中的应用,我们研究了3-芳基氧化吲哚与苯基烯基砜的Michael加成反应。研究结果表明,以磺酰胺为多氢键给体的奎宁硫脲催化剂能够有效地催化该反应,以中等到较好的收率(52-86% yield)和优秀的对映选择性(83-98%ee)得到带有季碳原子的多取代的手性氧化吲哚化合物。
此外,该催化剂还能够有效地催化异氰基乙酸酯与靛红的[3+2]环加成反应,以中等到优秀的收率(53-99% yield),优秀的非对映选择性(up to 99:1 dr)和优秀的对映选择性(up to 97% ee)得到手性螺[氧化吲哚-3,5'-嗯哗啉]化合物,有关该反应底物的拓展及结构优化还在进行之中。
This thesis focused on the synthesis of cinchona alkaloid derived bifunctional amine-thiourea catalysts bearing multiple hydrogen-bonding donors, and their initial applications in catalytic asymmetric reactions. The catalysts have been synthesized from quinine or quinidine by the one-pot reaction with triphenylphosphine, diisopropyl azodicarboxylate (DIAD) and diphenylphosphoryl azide (DPPA), then treated with triphenylphosphine and carbon disulfide to form cinchona alkaloid derived isothiocyanate, which was converted to the corresponding catalysts after the reaction with various different ammes.
In order to illustrate the application of this kind of catalysts, a highly enantioselective Michael addition reaction of 3-aryl-N-Boc oxindoles to phenyl vinyl sulfone has been developed by using quinine derived bifunctional tertiary amine-thiourea-bearing sulfonamide as multiple hydrogen-bonding donor organocatalyst. The reaction scope is substantial and a number of oxindoles could be successfully applied to give the corresponding multifunctional chiral oxindole compounds bearing an all carbon-substituted quaternary stereocenter in moderate to good yields (52-86%) with good to excellent enantioselectivities (83-98% ee).
Moreover, the quinine derived bifunctional tertiary amine-thiourea-bearing sulfonamide as multiple hydrogen-bonding donor organocatalyst was also found to be effective catalyst for the asymmetric addition reaction of isocyanoacetate to isatins, affording the optical spirooxindoles with moderate to good yield (53-99%), excellent diastereoselectivity (up to 99:1 dr) and excellent enantioselectivity (up to 97% ee).
为了考察该类催化剂在不对称合成中的应用,我们研究了3-芳基氧化吲哚与苯基烯基砜的Michael加成反应。研究结果表明,以磺酰胺为多氢键给体的奎宁硫脲催化剂能够有效地催化该反应,以中等到较好的收率(52-86% yield)和优秀的对映选择性(83-98%ee)得到带有季碳原子的多取代的手性氧化吲哚化合物。
此外,该催化剂还能够有效地催化异氰基乙酸酯与靛红的[3+2]环加成反应,以中等到优秀的收率(53-99% yield),优秀的非对映选择性(up to 99:1 dr)和优秀的对映选择性(up to 97% ee)得到手性螺[氧化吲哚-3,5'-嗯哗啉]化合物,有关该反应底物的拓展及结构优化还在进行之中。
This thesis focused on the synthesis of cinchona alkaloid derived bifunctional amine-thiourea catalysts bearing multiple hydrogen-bonding donors, and their initial applications in catalytic asymmetric reactions. The catalysts have been synthesized from quinine or quinidine by the one-pot reaction with triphenylphosphine, diisopropyl azodicarboxylate (DIAD) and diphenylphosphoryl azide (DPPA), then treated with triphenylphosphine and carbon disulfide to form cinchona alkaloid derived isothiocyanate, which was converted to the corresponding catalysts after the reaction with various different ammes.
In order to illustrate the application of this kind of catalysts, a highly enantioselective Michael addition reaction of 3-aryl-N-Boc oxindoles to phenyl vinyl sulfone has been developed by using quinine derived bifunctional tertiary amine-thiourea-bearing sulfonamide as multiple hydrogen-bonding donor organocatalyst. The reaction scope is substantial and a number of oxindoles could be successfully applied to give the corresponding multifunctional chiral oxindole compounds bearing an all carbon-substituted quaternary stereocenter in moderate to good yields (52-86%) with good to excellent enantioselectivities (83-98% ee).
Moreover, the quinine derived bifunctional tertiary amine-thiourea-bearing sulfonamide as multiple hydrogen-bonding donor organocatalyst was also found to be effective catalyst for the asymmetric addition reaction of isocyanoacetate to isatins, affording the optical spirooxindoles with moderate to good yield (53-99%), excellent diastereoselectivity (up to 99:1 dr) and excellent enantioselectivity (up to 97% ee).
引文
[1]Eder, U; Sauer, G; Wiechert, R. Total synthesis of optically active steroids. New type of asymmetric cyclization to optically active steroid CD partial structures. Angew. Chem. 1971,83,492-493; Angew. Chem. Int. Ed.1971,10,496-497.
[2]Hajos, Z. G.; Parrish, D. R. Asymmetric synthesis of bicyclic intermediates of natural product chemistry. J. Org. Chem.1974,39,1615-1621.
[3]List, B.; Lerner, R. A.; Barbas Ⅲ, C. F. Proline-catalyzed direct asymmetric aldol reactions. J. Am. Chem. Soc.2000,122,2395-2396.
[4]Ahrendt, K. A.; Borths, C. J.; MacMillan, D. W. C. New Strategies for Organic Catalysis:The first highly enantioselective organocatalytic Diels-Alder reaction. J. Am. Chem. Soc.2000,122,4243-4244.
[5]Daisuke Uraguchi; Masahiro Terada. Chiral Br(?)nsted Acid-Catalyzed Direct Mannich Reactions via Electrophilic Activation. J. Am. Chem. Soc.2004,126,5356-5357.
[6]Takahiko Akiyama; Junji Itoh; Koji Yokota; Kohei Fuchibe. Enantioselective Mannich-Type Reaction Catalyzed by a Chiral Br(?)nsted Acid. Angew. Chem. Int. Ed.2004, 43,1566-1568.
[7]Matthew S. Sigman; Eric N. Jacobsen. Schiff Base Catalysts for the Asymmetric Strecker Reaction Identified and Optimized from Parallel Synthetic Libraries. J. Am. Chem. Soc.1998,120,4901-4902.
[8]Tomotaka Okino; Yasutaka Hoashi; Yoshiji Takemoto. Enantioselective Michael Reaction of Malonates to Nitroolefins Catalyzed by Bifunctional Organocatalysts. J. Am. Chem. Soc.2003,125,12672-12673.
[9]Yasutaka Hoashi; Tomotaka Okino; Yoshiji Takemoto. Enantioselective Michael Addition to α,β-Unsaturated Imides Catalyzed by a Bifunctional Organocatalyst. Angew. Chem. Int. Ed.2005,44,4032-4035.
[10]Douglas E. Fuerst; Eric N.Jacobsen. Thiourea-Catalyzed Enantioselective Cyanosily-lation of Ketones. J. Am. Chem. Soc.2005,127,8964-8965.
[11]Yousuke Yamaoka; Hideto Miyabe; Yoshiji Takemoto. Catalytic Enantioselective Petasis-Type Reaction of Quinolines Catalyzed by a Newly Designed Thiourea Catalyst. J. Am. Chem. Soc.2007,129,6686-6687.
[12]Nolwenn J.A.Martin; Lidia Ozores; Benjamin List. Organocatalytic Asymmetric Transfer Hydrogenation of Nitroolefins. J. Am. Chem.2007,129,8976-8977.
[13]Tian-Yu Liu; Rui Li; Qian Chai; Ying-Chun Chen. Enantioselective Michael Addition of α-Substituted Cyanoacetates to Vinyl Ketones Catalyzed by Bifunctional Organocatalysts. Chem. Eur. J.2007,13,319-327.
[14]Liansuo Zu; Hexin Xie; Hao Li; Jian Wang; Wei Jiang; Wei Wang. Chiral Amine Thiourea-Promoted Enantioselective Domino Michael-Aldol Reactions between 2-Mercaptobenzaldehydes and Maleimides. Adv. Synth. Catal.2007,349,1882-1886.
[15]Tommy Bui; Salahuddin Syed; Carlos F. BarbasⅢ. Thiourea-Catalyzed Highly Enantio-and Diastereoselective Addition of Oxindoles to Nitroolefins:Application to the Formal Synthesis of (+)-Physostigmine. J. Am. Chem. Soc.2009,131,8758-8759.
[16]Xin Li; Sanzhong Luo; Jin-PeiCheng. Asymmetric Michael Addition Reaction of 3-Substituted Oxindoles to Nitroolefins Catalyzed by a Chiral Alkyl-Substituted Thiourea Catalyst. Adv. Synth. Catal.2010,352,416-424.
[17]Jian Wang; Hao Li; Xinhong Yu; Liansuo Zu; Wei Wang. Chiral Binaphthyl-Derived Amine-Thiourea Organocatalyst-Promoted Asymmetric Morita-Baylis-Hillman Reaction. Org Lett.2005,7,4293-4296.
[18]Jian Wang; Hao Li; Wenhu Duan; Liansuo Zu; Wei Wang. Organocatalytic Asymmetric Michael Addition of 2,4-Pentandioneto Nitroolefins. Org. Lett.2005,7,4713-4716.
[19]Patrizia Galzerano; Giorgio Bencivenni; Paolo Melchiorre. Asymmetric Iminium Ion Catalysis with a Novel Bifunctional Primary Amine Thiourea:Controlling Adjacent Quaternary and Tertiary Stereocenters. Chem. Eur. J.2009,15,7846-7849.
[20]Constantinos Rabalakos; William D. Wulff. Enantioselective Organocatalytic Direct Michael Addition of Nitroalkanes to Nitroalkenes Promoted by a Unique Bifunctional DMAP-Thiourea. J. Am. Chem. Soc.2008,130,13524-13525.
[21]Constantinos Rampalakos; WilliamD. Wulff. A Novel Bis-Thiourea Organocatalyst for the Asymmetric Aza-Henry Reaction. Adv. Synth. Catal.2008,350,1785-1790.
[22]Tian-Yu Liu; Jun Long; Ying-Chun Chen. Enantioselective construction of quaternary carbon centre catalysed by bifunctional organocatalyst. Org. Biomol. Chem.2006,4, 2097-2099.
[23]Bo Han; Qing-Ping Liu; Rui Li; Ying-Chun Chen. Discovery of Bifunctional Thiourea/ Secondary-Amine Organocatalysts for the Highly Stereoselective Nitro-Mannich Reaction of α-Substituted Nitroacetates. Chem. Eur. J.2008,14,8094-8097.
[24]Francesca Marini; Silvia Sternativo; Marcello Tieccoa. Enantioselective Organocatalytic Michael Addition of α-Substituted Cyanoacetates to α,β-Unsaturated Selenones. Adv. Synth. Catal.2009,351,103-106.
[25]Yu-Hua Liao; Xiong-Li Liu; Wei-Cheng Yuan. 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.
[26]Xiong-Li Liu; Yu-Hua Liao; Wei-Cheng Yuan. Organocatalytic Enantioselective Hydroxymethylation of Oxindoles with Paraformaldehyde as C1 Unit. J. Org. Chem. 2010,75,4872-4875.
[27]Jinxing Ye; Darren J. Dixon; Peter S.Hynes. Enantioselective organocatalytic Michael addition of malonate esters to nitro olefins using bifunctional cinchonine derivatives. Chem. Commun.2005,4481-4483.
[28]Qunsheng Guo; Mayur Bhanushali; Cong-Gui Zhao. Quinidine Thiourea-Catalyzed Aldol Reaction of Unactivated Ketones:Highly Enantioselective Synthesis of 3-Alkyl-3-hydroxy-indolin-2-ones. Angew. Chem. Int. Ed.2010,49,9460-9464.
[29]BenedekVakulya; Antal Csampai; Tibor Soos. Highly Enantioselective Conjugate Addition of Nitromethane to Chalcones Using Bifunctiona 1Cinchona Organocatalysts. Org. Lett.,2005,7,1967-1969.
[30]Jian Wang; Wenhu Duan; Wei Wang. Organocatalytic Enantioselective Conjugate Additions to Enones. J. Am. Chem. Soc.2006,128,12652-12653.
[31]Jun Song; Yi Wang; Li Deng. The Mannich Reaction of Malonates with Simple Imines Catalyzed by Bifunctional Cinchona Alkaloids:Enantioselective Synthesis of β-Amino Acids. J. Am. Chem. Soc.2006,128,6048-6049.
[32]Yong-Qiang Wang; Jun Song; Li Deng. Asymmetric Friedel- Crafts Reaction of Indoles with Imines by an Organic Catalyst. J. Am. Chem. Soc.2006,128,8156-8157.
[33]Tian-Yu Liu; Hai-Lei Cui; Ying-Chun Chen; Organocatalytic asymmetric Friedel-Crafts alkylation/cascade reaction sofnaphthols and nitroolefins. Chem. Commun.2007,2228-2230.
[34]Claudio Gioia; Agnes Hauville; Alfredo Ricci. Organocatalytic Asymmetric Diels-Alder Reactions of 3-Vinylindoles. Angew. Chem. Int. Ed.2008,47,9236-9239.
[35]张志海,董秀琴,滕怀龙,陶海燕,王春江.含多氢键给体的氨基-硫脲类有机小分子催化剂的设计、合成及应用.科学通报,2009,54,3407-3419.
[36]Wang C J; Zhang Z H; Dong X Q; Chiral amine-thioureas bearing multiple hydrogen bonding donors:highly efficient organocatalysts for asymmetric Michael addition of acetylacetone to nitroolefin. Chem Commun.2008,12,1431-1433.
[37]Deng H Q, Teng H L, 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.
[38]Zhi-Hai Zhang; Xiu-Qin Dong; Chun-Jiang Wang. Asymmetric amination of cyclic β-keto esters catalyzed by amine-thiourea bearing multiple hydrogen bonding donors. ARKIVOC,2011,2,137-150.
[39](a) Shibata, N.; Suzuki, E.; Asahi, T.; Shiro, M. Enantioselective Fluorination Mediated by Cinchona Alkaloid Derivatives/Selectfluor Combinations:Reaction Scope and Structural Information for N-Fluorocinchona Alkaloids. J. Am. Chem. Soc.2001,123, 7001-7009. (b) Shibata, N.; Kohno, J.; Takai, K.; Ishimaru, T.; Nakamura, S.; Toru, T. Kanemasa, S. Highly Enantioselective Catalytic Fluorination and Chlorination Reactions of Carbonyl Compounds Capable of Two-Point Binding. Angew. Chem. Int. Ed.2005,44,4204-4207.
[40](a) Ishimaru, T.; Shibata, N.; Nagai, J.; Nakamura, S.; Toru, T.; Kanemasa, S. Lewis Acid-Catalyzed Enantioselective Hydroxylation Reactions of Oxindoles and β-Keto Esters Using DBFOX Ligand. J. Am. Chem. Soc.2006,128,16488-16489. (b) Sano, D.; Nagata, K.; Itoh, T. Catalytic Asymmetric Hydroxylation of Oxindoles by Molecular Oxygen Using a Phase-Transfer Catalyst. Org. Lett.2008,10,1593-1595.
[41](a) Zhigang Yang; Zhen Wang; XiaomingFeng. Highly Enantioselective Synthesis of 3-Amino-2-oxindole Derivatives:Catalytic Asymmetric a-Amination of 3-Substituted 2-Oxindoles with a Chiral Scandium Complex. Chem. Eur. J.2010,16,6632-6637. (b) Tommy Bui; Gloria Hernandez-Torres; Carlos F.Barbas III. Highly Enantioselective Organocatalytic a-Amination Reactions of Aryl Oxindoles:Developing Designer Multifunctional Alkaloid Catalysts. Org. Lett.2010,12,5696-5699. (c) Cheng, L.; Liu, L.; Wang, D.; Chen, Y. J. Highly Enantioselective and Organocatalytic α-Amination of 2-Oxindoles. Org. Lett.2009,11,3874-3877.
[42](a) Ogawa, S.; Shibata, N.; Inagaki, J.; Nakamura, S.; Toru, T.; Shiro, M. Cinchona-Alkaloid-Catalyzed Enantioselective Direct Aldol-Type Reaction of Oxindoles with Ethyl Trifluoropyruvate. Angew. Chem. Int. Ed.2007,46,8666-8669. (b) Guo, Q. S.; Bhanushali, M.; Zhao, C. G. Quinidine Thiourea-Catalyzed Aldol Reaction of Unactivated Ketones:Highly Enantioselective Synthesis of 3-Alkyl-3-hydroxy-indolin-2-ones. Angew. Chem. Int. Ed.2010,49,1-6. (c) Liu, X. L.; Liao, Y. H.; Wu, Z. J.; Cun, L. F.; Zhang, X. M.; Yuan, W. C. Organocatalytic Enantioselective Hydroxymethylation of Oxindoles with Paraform aldehyde as C1 Unit. J. Org. Chem.2010,75,4872-4875.
[43](a) Tian, X.; Jiang, K.; Peng, J.; Du, W.; Chen, Y. C. Organocatalytic Stereoselective Mannich Reaction of 3-Substituted Oxindoles. Org. Lett.2008,10,3583-3586. (b) 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. (c) 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.
[44](a) Barry M.Trost; Yong Zhang. Catalytic Double Stereoinduction in Asymmetric Allylic Alkylation of Oxindoles. Chem. Eur. J.2010,16,296-303. (b) Barry M.Trost; Yong Zhang. Molybdenum-Catalyzed Asymmetric Allylic Alkylation of 3-Alkyl oxindoles:Reaction Development and Applications. Chem. Eur. J.2011,17,2916-2922. (c) Kun Jiang; Jing Peng; Ying-Chun Chen. Organocatalytic asymmetric allylic alkylation of oxindoles with Morita-Baylis-Hillman carbonates. Chem. Commun.2009, 3955-3957.
[45](a) Xin Li; Bo Zhang; Jin-Pei Cheng. Asymmetric Michael Addition Reaction of 3-Substituted Oxindoles to Nitroolefins Catalyzed by a Chiral Alkyl-Substituted Thiourea Catalyst. Adv. Synth. Catal.2010,352,416-424. (b) Xin Li; Sanzhong Luo; Jin-Pei Cheng. Asymmetric Conjugate Addition of Oxindoles to 2-Chloroacrylonitrile: A Highly Effective Organocatalytic Strategy for Simultaneous Construction of 1,3-Nonadjacent Stereocenters Leading to Chiral Pyrroloindolines. Chem. Eur. J.2010, 16,14290-14294. (c) 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. (d) Q Zhu; Y Lu. Stereocontrolled Creation of All-Carbon Quaternary Stereocenters by Organocatalytic Conjugate Addition of Oxindoles to Vinyl Sulfone. Angew. Chem. Int. Ed.2010,49, 7753-7756. (e) X Li; Z. G Xi; S. Z Luo; J. P Cheng. Asymmetric Michael addition reaction of 3-substituted-N-Boc oxindoles to activated terminal alkenes catalyzed by a bifunctional tertiary-amine thiourea catalyst. Org. Biomol. Chem.2010,8,77-82. (f) Shu-Wen Duan; Jia-Rong Chen; Wen-Jing Xiao; Facile Synthesis of Enantioenriched CY-Tetrasubstituted a-Amino Acid Derivatives via an Asymmetric Nucleophilic Addition/Protonation Cascade. Org. Lett.2011,13,2290-2293. (g) Fabio Pescisioli; Xu Tian; Paolo Melchiorre. Organocatalytic Asymmetric Conjugate Additions of Oxindoles and Benzofuranones to Cyclic Enones. Synlett,2010,11,1704-1708. (h) Wangsheng Sun; Liang Hong; Rui Wang. Asymmetric construction of quaternary stereocenters by direct conjugate addition of oxindoles to enone. Tetrahedron:Asymmetry,2010,21, 2493-2497. (i) Matthias H. Freund; Svetlana B. Tsogoeva. L-Proline-Catalyzed Asymmetric Michael Addition of 2-Oxindoles to Enones:A Convenient Access to Oxindoles with a Quaternary Stereocenter. Synlett,2011,4,503-507.
[46]Ito, Y.; Sawamura, M.; Kobayashi, M.; Hayashi, T. Asymmetric aldol reaction of a-isocyanoacetamides with aldehydes catalyzed by a chiral ferrocenylphosphine-gold(Ⅰ) complex. Tetrahedron Lett.1988,29,6321-6324.
[47]Masaya Sawamura; Hitoshi Hamashima; Yoshihiko Ito. The Asymmetric Aldol Reaction of Tosylmethyl Isocyanide and Aldehydes Catalyzed by ChiralSilver(Ⅰ) Complexes. J. Org. Chem.1990,55,5935-5936.
[48]James M. Longmire; Xumu Zhang. Synthesis and X-ray Crystal Structures of Palladium(II) and Platinum(II) Complexes of the PCP-Type Chiral Tridentate Ligand (1R,1R)-1,3-Bis[1-(diphenylphosphino)ethyl]benzene. Use in the Asymmetric Aldol Reaction of Methyl Isocyanoacetate and Aldehydes. Organometallics,1998,17, 4374-4379.
[49]Filippo Sladojevich; Andrea Trabocchi; Darren J. Dixon. A New Family of Cinchona-Derived Amino Phosphine Precatalysts:Application to the Highly Enantio- and Diastereoselective Silver-Catalyzed Isocyanoacetate Aldol Reaction. J. Am. Chem. Soc. 2011,735,1710-1713.
[50]Chang Guo; Meng-Xia Xue; Liu-Zhu Gong; Organocatalytic Asymmetric Formal [3+2] Cycloaddition Reaction of Isocyanoesters to Nitroolefins Leading to Highly Optically Active Dihydropyrroles. Angew. Chem. Int. Ed.2008,47,3414-3417.
[51]Meng-Xia Xue; Chang Guo; Liu-Zhu Gong. Asymmetric Synthesis of Chiral Oxazolines by Organocatalytic Cyclization of α-Aryl Isocyanoesters with Aldehydes. Synlett,2009,13,2191-2197.
[52]David Monge; Kim L.Jensen; Karl Anker J(?)rgensen. Synthesis of 1,2,4-Triazolines: Base-Catalyzed Hydrazination/Cyclization Cascade of α-Isocyano Esters and Amides. Org.Lett.2011,13,328-331.
[53]Jin Song; Chang Guo; Liu-Zhu Gong. Asymmetric Formal [3+2] Cycloaddition Reaction of Isocyanoesters to 2-Oxobutenoate Esters by a Multifunctional Chiral Silver Catalyst. Chem. Eur. J.2011,17,7786-7790.
[54](a) Qiang Wei; Liu-Zhu Gong. Organocatalytic Asymmetric Formal [4+2] Cycloaddition for the Synthesis of Spiro[4-cyclohexanone-1,3'-oxindoline] Derivatives in High Optical Purity. Org. Lett.,2010,12,1008-1011. (b) Yun Zhang; James S. Panek. Stereocontrolled Synthesis of Spirooxindoles through Lewis Acid-Promoted [5+2]-Annulation of Chiral Silyl Alcohols. Org. Lett.2009,11,3366-3369.
[55](a) Bernhard Westermann; Muhammad Ayaz; Sander S. van Berkel. Enantiodivergent Organocascade Reactions. Angew. Chem. Int. Ed.2010,49,846-849. (b) Giorgio Bencivenni; Li-Yuan Wu; Paolo Melchiorre. Targeting Structural and Stereochemical Complexity by Organocascade Catalysis:Construction of Spirocyclic Oxindoles Having Multiple Stereocenters. Angew. Chem. Int. Ed.2009,48,7200-7203. (c) Thelagathoti Hari Babu; A. Abragam Joseph; Paramasivan T. Perumal. A novel method for the synthesis of functionalized spirocyclicoxindole by one-pot tandem reaction of vinyl malononitriles with isatylidene malononitriles. Tetrahedron Lett.2010,51,994-996.
[56]M. Paola Castaldi; Dawn M. Troast; John A. Porco, Jr. Stereoselective Synthesis of Spirocyclic Oxindoles via Prins Cyclizations. Org. Lett.2009,11,3362-3365.
[57](a) Ryo Shintani; Shin-ya Hayashi; Tamio Hayashi. Stereoselective Synthesis of Spirooxindoles by Palladium-Catalyzed Decarboxylative Cyclization of γ-Methylidene-δ-valerolactones with Isatins. Org. Lett.2009,11,3574-3576. (b) Chunliang Lu; Qing Xiao; Paul E. Floreancig. Stereoselective Synthesis of Spirooxindole Amides through Nitrile Hydrozirconation. Org. Lett.2010,12,5112-5115. (c) Xianxing Jiang; Yiming Cao; Rui Wang. A Unique Approach to the Concise Synthesis of Highly Optically Active Spirooxazolines and the Discovery of a More Potent Oxindole-Type Phytoalexin Analogue. J. Am. Chem. Soc.2010,132,15328-15333. (d) Sergery G. Zavgorodny. A novel type of anhydronucleusides to model syn-conformers of natural nucleosides. Tetrahedron Lett.1981.22,3003-3006.
[58]Joseph J. Badillo; Gary E. Arevalo; Annaliese K. Franz. Titanium-Catalyzed Stereoselective Synthesis of Spirooxindole Oxazolines. Org. Lett.2011,13,418-421.
[2]Hajos, Z. G.; Parrish, D. R. Asymmetric synthesis of bicyclic intermediates of natural product chemistry. J. Org. Chem.1974,39,1615-1621.
[3]List, B.; Lerner, R. A.; Barbas Ⅲ, C. F. Proline-catalyzed direct asymmetric aldol reactions. J. Am. Chem. Soc.2000,122,2395-2396.
[4]Ahrendt, K. A.; Borths, C. J.; MacMillan, D. W. C. New Strategies for Organic Catalysis:The first highly enantioselective organocatalytic Diels-Alder reaction. J. Am. Chem. Soc.2000,122,4243-4244.
[5]Daisuke Uraguchi; Masahiro Terada. Chiral Br(?)nsted Acid-Catalyzed Direct Mannich Reactions via Electrophilic Activation. J. Am. Chem. Soc.2004,126,5356-5357.
[6]Takahiko Akiyama; Junji Itoh; Koji Yokota; Kohei Fuchibe. Enantioselective Mannich-Type Reaction Catalyzed by a Chiral Br(?)nsted Acid. Angew. Chem. Int. Ed.2004, 43,1566-1568.
[7]Matthew S. Sigman; Eric N. Jacobsen. Schiff Base Catalysts for the Asymmetric Strecker Reaction Identified and Optimized from Parallel Synthetic Libraries. J. Am. Chem. Soc.1998,120,4901-4902.
[8]Tomotaka Okino; Yasutaka Hoashi; Yoshiji Takemoto. Enantioselective Michael Reaction of Malonates to Nitroolefins Catalyzed by Bifunctional Organocatalysts. J. Am. Chem. Soc.2003,125,12672-12673.
[9]Yasutaka Hoashi; Tomotaka Okino; Yoshiji Takemoto. Enantioselective Michael Addition to α,β-Unsaturated Imides Catalyzed by a Bifunctional Organocatalyst. Angew. Chem. Int. Ed.2005,44,4032-4035.
[10]Douglas E. Fuerst; Eric N.Jacobsen. Thiourea-Catalyzed Enantioselective Cyanosily-lation of Ketones. J. Am. Chem. Soc.2005,127,8964-8965.
[11]Yousuke Yamaoka; Hideto Miyabe; Yoshiji Takemoto. Catalytic Enantioselective Petasis-Type Reaction of Quinolines Catalyzed by a Newly Designed Thiourea Catalyst. J. Am. Chem. Soc.2007,129,6686-6687.
[12]Nolwenn J.A.Martin; Lidia Ozores; Benjamin List. Organocatalytic Asymmetric Transfer Hydrogenation of Nitroolefins. J. Am. Chem.2007,129,8976-8977.
[13]Tian-Yu Liu; Rui Li; Qian Chai; Ying-Chun Chen. Enantioselective Michael Addition of α-Substituted Cyanoacetates to Vinyl Ketones Catalyzed by Bifunctional Organocatalysts. Chem. Eur. J.2007,13,319-327.
[14]Liansuo Zu; Hexin Xie; Hao Li; Jian Wang; Wei Jiang; Wei Wang. Chiral Amine Thiourea-Promoted Enantioselective Domino Michael-Aldol Reactions between 2-Mercaptobenzaldehydes and Maleimides. Adv. Synth. Catal.2007,349,1882-1886.
[15]Tommy Bui; Salahuddin Syed; Carlos F. BarbasⅢ. Thiourea-Catalyzed Highly Enantio-and Diastereoselective Addition of Oxindoles to Nitroolefins:Application to the Formal Synthesis of (+)-Physostigmine. J. Am. Chem. Soc.2009,131,8758-8759.
[16]Xin Li; Sanzhong Luo; Jin-PeiCheng. Asymmetric Michael Addition Reaction of 3-Substituted Oxindoles to Nitroolefins Catalyzed by a Chiral Alkyl-Substituted Thiourea Catalyst. Adv. Synth. Catal.2010,352,416-424.
[17]Jian Wang; Hao Li; Xinhong Yu; Liansuo Zu; Wei Wang. Chiral Binaphthyl-Derived Amine-Thiourea Organocatalyst-Promoted Asymmetric Morita-Baylis-Hillman Reaction. Org Lett.2005,7,4293-4296.
[18]Jian Wang; Hao Li; Wenhu Duan; Liansuo Zu; Wei Wang. Organocatalytic Asymmetric Michael Addition of 2,4-Pentandioneto Nitroolefins. Org. Lett.2005,7,4713-4716.
[19]Patrizia Galzerano; Giorgio Bencivenni; Paolo Melchiorre. Asymmetric Iminium Ion Catalysis with a Novel Bifunctional Primary Amine Thiourea:Controlling Adjacent Quaternary and Tertiary Stereocenters. Chem. Eur. J.2009,15,7846-7849.
[20]Constantinos Rabalakos; William D. Wulff. Enantioselective Organocatalytic Direct Michael Addition of Nitroalkanes to Nitroalkenes Promoted by a Unique Bifunctional DMAP-Thiourea. J. Am. Chem. Soc.2008,130,13524-13525.
[21]Constantinos Rampalakos; WilliamD. Wulff. A Novel Bis-Thiourea Organocatalyst for the Asymmetric Aza-Henry Reaction. Adv. Synth. Catal.2008,350,1785-1790.
[22]Tian-Yu Liu; Jun Long; Ying-Chun Chen. Enantioselective construction of quaternary carbon centre catalysed by bifunctional organocatalyst. Org. Biomol. Chem.2006,4, 2097-2099.
[23]Bo Han; Qing-Ping Liu; Rui Li; Ying-Chun Chen. Discovery of Bifunctional Thiourea/ Secondary-Amine Organocatalysts for the Highly Stereoselective Nitro-Mannich Reaction of α-Substituted Nitroacetates. Chem. Eur. J.2008,14,8094-8097.
[24]Francesca Marini; Silvia Sternativo; Marcello Tieccoa. Enantioselective Organocatalytic Michael Addition of α-Substituted Cyanoacetates to α,β-Unsaturated Selenones. Adv. Synth. Catal.2009,351,103-106.
[25]Yu-Hua Liao; Xiong-Li Liu; Wei-Cheng Yuan. 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.
[26]Xiong-Li Liu; Yu-Hua Liao; Wei-Cheng Yuan. Organocatalytic Enantioselective Hydroxymethylation of Oxindoles with Paraformaldehyde as C1 Unit. J. Org. Chem. 2010,75,4872-4875.
[27]Jinxing Ye; Darren J. Dixon; Peter S.Hynes. Enantioselective organocatalytic Michael addition of malonate esters to nitro olefins using bifunctional cinchonine derivatives. Chem. Commun.2005,4481-4483.
[28]Qunsheng Guo; Mayur Bhanushali; Cong-Gui Zhao. Quinidine Thiourea-Catalyzed Aldol Reaction of Unactivated Ketones:Highly Enantioselective Synthesis of 3-Alkyl-3-hydroxy-indolin-2-ones. Angew. Chem. Int. Ed.2010,49,9460-9464.
[29]BenedekVakulya; Antal Csampai; Tibor Soos. Highly Enantioselective Conjugate Addition of Nitromethane to Chalcones Using Bifunctiona 1Cinchona Organocatalysts. Org. Lett.,2005,7,1967-1969.
[30]Jian Wang; Wenhu Duan; Wei Wang. Organocatalytic Enantioselective Conjugate Additions to Enones. J. Am. Chem. Soc.2006,128,12652-12653.
[31]Jun Song; Yi Wang; Li Deng. The Mannich Reaction of Malonates with Simple Imines Catalyzed by Bifunctional Cinchona Alkaloids:Enantioselective Synthesis of β-Amino Acids. J. Am. Chem. Soc.2006,128,6048-6049.
[32]Yong-Qiang Wang; Jun Song; Li Deng. Asymmetric Friedel- Crafts Reaction of Indoles with Imines by an Organic Catalyst. J. Am. Chem. Soc.2006,128,8156-8157.
[33]Tian-Yu Liu; Hai-Lei Cui; Ying-Chun Chen; Organocatalytic asymmetric Friedel-Crafts alkylation/cascade reaction sofnaphthols and nitroolefins. Chem. Commun.2007,2228-2230.
[34]Claudio Gioia; Agnes Hauville; Alfredo Ricci. Organocatalytic Asymmetric Diels-Alder Reactions of 3-Vinylindoles. Angew. Chem. Int. Ed.2008,47,9236-9239.
[35]张志海,董秀琴,滕怀龙,陶海燕,王春江.含多氢键给体的氨基-硫脲类有机小分子催化剂的设计、合成及应用.科学通报,2009,54,3407-3419.
[36]Wang C J; Zhang Z H; Dong X Q; Chiral amine-thioureas bearing multiple hydrogen bonding donors:highly efficient organocatalysts for asymmetric Michael addition of acetylacetone to nitroolefin. Chem Commun.2008,12,1431-1433.
[37]Deng H Q, Teng H L, 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.
[38]Zhi-Hai Zhang; Xiu-Qin Dong; Chun-Jiang Wang. Asymmetric amination of cyclic β-keto esters catalyzed by amine-thiourea bearing multiple hydrogen bonding donors. ARKIVOC,2011,2,137-150.
[39](a) Shibata, N.; Suzuki, E.; Asahi, T.; Shiro, M. Enantioselective Fluorination Mediated by Cinchona Alkaloid Derivatives/Selectfluor Combinations:Reaction Scope and Structural Information for N-Fluorocinchona Alkaloids. J. Am. Chem. Soc.2001,123, 7001-7009. (b) Shibata, N.; Kohno, J.; Takai, K.; Ishimaru, T.; Nakamura, S.; Toru, T. Kanemasa, S. Highly Enantioselective Catalytic Fluorination and Chlorination Reactions of Carbonyl Compounds Capable of Two-Point Binding. Angew. Chem. Int. Ed.2005,44,4204-4207.
[40](a) Ishimaru, T.; Shibata, N.; Nagai, J.; Nakamura, S.; Toru, T.; Kanemasa, S. Lewis Acid-Catalyzed Enantioselective Hydroxylation Reactions of Oxindoles and β-Keto Esters Using DBFOX Ligand. J. Am. Chem. Soc.2006,128,16488-16489. (b) Sano, D.; Nagata, K.; Itoh, T. Catalytic Asymmetric Hydroxylation of Oxindoles by Molecular Oxygen Using a Phase-Transfer Catalyst. Org. Lett.2008,10,1593-1595.
[41](a) Zhigang Yang; Zhen Wang; XiaomingFeng. Highly Enantioselective Synthesis of 3-Amino-2-oxindole Derivatives:Catalytic Asymmetric a-Amination of 3-Substituted 2-Oxindoles with a Chiral Scandium Complex. Chem. Eur. J.2010,16,6632-6637. (b) Tommy Bui; Gloria Hernandez-Torres; Carlos F.Barbas III. Highly Enantioselective Organocatalytic a-Amination Reactions of Aryl Oxindoles:Developing Designer Multifunctional Alkaloid Catalysts. Org. Lett.2010,12,5696-5699. (c) Cheng, L.; Liu, L.; Wang, D.; Chen, Y. J. Highly Enantioselective and Organocatalytic α-Amination of 2-Oxindoles. Org. Lett.2009,11,3874-3877.
[42](a) Ogawa, S.; Shibata, N.; Inagaki, J.; Nakamura, S.; Toru, T.; Shiro, M. Cinchona-Alkaloid-Catalyzed Enantioselective Direct Aldol-Type Reaction of Oxindoles with Ethyl Trifluoropyruvate. Angew. Chem. Int. Ed.2007,46,8666-8669. (b) Guo, Q. S.; Bhanushali, M.; Zhao, C. G. Quinidine Thiourea-Catalyzed Aldol Reaction of Unactivated Ketones:Highly Enantioselective Synthesis of 3-Alkyl-3-hydroxy-indolin-2-ones. Angew. Chem. Int. Ed.2010,49,1-6. (c) Liu, X. L.; Liao, Y. H.; Wu, Z. J.; Cun, L. F.; Zhang, X. M.; Yuan, W. C. Organocatalytic Enantioselective Hydroxymethylation of Oxindoles with Paraform aldehyde as C1 Unit. J. Org. Chem.2010,75,4872-4875.
[43](a) Tian, X.; Jiang, K.; Peng, J.; Du, W.; Chen, Y. C. Organocatalytic Stereoselective Mannich Reaction of 3-Substituted Oxindoles. Org. Lett.2008,10,3583-3586. (b) 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. (c) 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.
[44](a) Barry M.Trost; Yong Zhang. Catalytic Double Stereoinduction in Asymmetric Allylic Alkylation of Oxindoles. Chem. Eur. J.2010,16,296-303. (b) Barry M.Trost; Yong Zhang. Molybdenum-Catalyzed Asymmetric Allylic Alkylation of 3-Alkyl oxindoles:Reaction Development and Applications. Chem. Eur. J.2011,17,2916-2922. (c) Kun Jiang; Jing Peng; Ying-Chun Chen. Organocatalytic asymmetric allylic alkylation of oxindoles with Morita-Baylis-Hillman carbonates. Chem. Commun.2009, 3955-3957.
[45](a) Xin Li; Bo Zhang; Jin-Pei Cheng. Asymmetric Michael Addition Reaction of 3-Substituted Oxindoles to Nitroolefins Catalyzed by a Chiral Alkyl-Substituted Thiourea Catalyst. Adv. Synth. Catal.2010,352,416-424. (b) Xin Li; Sanzhong Luo; Jin-Pei Cheng. Asymmetric Conjugate Addition of Oxindoles to 2-Chloroacrylonitrile: A Highly Effective Organocatalytic Strategy for Simultaneous Construction of 1,3-Nonadjacent Stereocenters Leading to Chiral Pyrroloindolines. Chem. Eur. J.2010, 16,14290-14294. (c) 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. (d) Q Zhu; Y Lu. Stereocontrolled Creation of All-Carbon Quaternary Stereocenters by Organocatalytic Conjugate Addition of Oxindoles to Vinyl Sulfone. Angew. Chem. Int. Ed.2010,49, 7753-7756. (e) X Li; Z. G Xi; S. Z Luo; J. P Cheng. Asymmetric Michael addition reaction of 3-substituted-N-Boc oxindoles to activated terminal alkenes catalyzed by a bifunctional tertiary-amine thiourea catalyst. Org. Biomol. Chem.2010,8,77-82. (f) Shu-Wen Duan; Jia-Rong Chen; Wen-Jing Xiao; Facile Synthesis of Enantioenriched CY-Tetrasubstituted a-Amino Acid Derivatives via an Asymmetric Nucleophilic Addition/Protonation Cascade. Org. Lett.2011,13,2290-2293. (g) Fabio Pescisioli; Xu Tian; Paolo Melchiorre. Organocatalytic Asymmetric Conjugate Additions of Oxindoles and Benzofuranones to Cyclic Enones. Synlett,2010,11,1704-1708. (h) Wangsheng Sun; Liang Hong; Rui Wang. Asymmetric construction of quaternary stereocenters by direct conjugate addition of oxindoles to enone. Tetrahedron:Asymmetry,2010,21, 2493-2497. (i) Matthias H. Freund; Svetlana B. Tsogoeva. L-Proline-Catalyzed Asymmetric Michael Addition of 2-Oxindoles to Enones:A Convenient Access to Oxindoles with a Quaternary Stereocenter. Synlett,2011,4,503-507.
[46]Ito, Y.; Sawamura, M.; Kobayashi, M.; Hayashi, T. Asymmetric aldol reaction of a-isocyanoacetamides with aldehydes catalyzed by a chiral ferrocenylphosphine-gold(Ⅰ) complex. Tetrahedron Lett.1988,29,6321-6324.
[47]Masaya Sawamura; Hitoshi Hamashima; Yoshihiko Ito. The Asymmetric Aldol Reaction of Tosylmethyl Isocyanide and Aldehydes Catalyzed by ChiralSilver(Ⅰ) Complexes. J. Org. Chem.1990,55,5935-5936.
[48]James M. Longmire; Xumu Zhang. Synthesis and X-ray Crystal Structures of Palladium(II) and Platinum(II) Complexes of the PCP-Type Chiral Tridentate Ligand (1R,1R)-1,3-Bis[1-(diphenylphosphino)ethyl]benzene. Use in the Asymmetric Aldol Reaction of Methyl Isocyanoacetate and Aldehydes. Organometallics,1998,17, 4374-4379.
[49]Filippo Sladojevich; Andrea Trabocchi; Darren J. Dixon. A New Family of Cinchona-Derived Amino Phosphine Precatalysts:Application to the Highly Enantio- and Diastereoselective Silver-Catalyzed Isocyanoacetate Aldol Reaction. J. Am. Chem. Soc. 2011,735,1710-1713.
[50]Chang Guo; Meng-Xia Xue; Liu-Zhu Gong; Organocatalytic Asymmetric Formal [3+2] Cycloaddition Reaction of Isocyanoesters to Nitroolefins Leading to Highly Optically Active Dihydropyrroles. Angew. Chem. Int. Ed.2008,47,3414-3417.
[51]Meng-Xia Xue; Chang Guo; Liu-Zhu Gong. Asymmetric Synthesis of Chiral Oxazolines by Organocatalytic Cyclization of α-Aryl Isocyanoesters with Aldehydes. Synlett,2009,13,2191-2197.
[52]David Monge; Kim L.Jensen; Karl Anker J(?)rgensen. Synthesis of 1,2,4-Triazolines: Base-Catalyzed Hydrazination/Cyclization Cascade of α-Isocyano Esters and Amides. Org.Lett.2011,13,328-331.
[53]Jin Song; Chang Guo; Liu-Zhu Gong. Asymmetric Formal [3+2] Cycloaddition Reaction of Isocyanoesters to 2-Oxobutenoate Esters by a Multifunctional Chiral Silver Catalyst. Chem. Eur. J.2011,17,7786-7790.
[54](a) Qiang Wei; Liu-Zhu Gong. Organocatalytic Asymmetric Formal [4+2] Cycloaddition for the Synthesis of Spiro[4-cyclohexanone-1,3'-oxindoline] Derivatives in High Optical Purity. Org. Lett.,2010,12,1008-1011. (b) Yun Zhang; James S. Panek. Stereocontrolled Synthesis of Spirooxindoles through Lewis Acid-Promoted [5+2]-Annulation of Chiral Silyl Alcohols. Org. Lett.2009,11,3366-3369.
[55](a) Bernhard Westermann; Muhammad Ayaz; Sander S. van Berkel. Enantiodivergent Organocascade Reactions. Angew. Chem. Int. Ed.2010,49,846-849. (b) Giorgio Bencivenni; Li-Yuan Wu; Paolo Melchiorre. Targeting Structural and Stereochemical Complexity by Organocascade Catalysis:Construction of Spirocyclic Oxindoles Having Multiple Stereocenters. Angew. Chem. Int. Ed.2009,48,7200-7203. (c) Thelagathoti Hari Babu; A. Abragam Joseph; Paramasivan T. Perumal. A novel method for the synthesis of functionalized spirocyclicoxindole by one-pot tandem reaction of vinyl malononitriles with isatylidene malononitriles. Tetrahedron Lett.2010,51,994-996.
[56]M. Paola Castaldi; Dawn M. Troast; John A. Porco, Jr. Stereoselective Synthesis of Spirocyclic Oxindoles via Prins Cyclizations. Org. Lett.2009,11,3362-3365.
[57](a) Ryo Shintani; Shin-ya Hayashi; Tamio Hayashi. Stereoselective Synthesis of Spirooxindoles by Palladium-Catalyzed Decarboxylative Cyclization of γ-Methylidene-δ-valerolactones with Isatins. Org. Lett.2009,11,3574-3576. (b) Chunliang Lu; Qing Xiao; Paul E. Floreancig. Stereoselective Synthesis of Spirooxindole Amides through Nitrile Hydrozirconation. Org. Lett.2010,12,5112-5115. (c) Xianxing Jiang; Yiming Cao; Rui Wang. A Unique Approach to the Concise Synthesis of Highly Optically Active Spirooxazolines and the Discovery of a More Potent Oxindole-Type Phytoalexin Analogue. J. Am. Chem. Soc.2010,132,15328-15333. (d) Sergery G. Zavgorodny. A novel type of anhydronucleusides to model syn-conformers of natural nucleosides. Tetrahedron Lett.1981.22,3003-3006.
[58]Joseph J. Badillo; Gary E. Arevalo; Annaliese K. Franz. Titanium-Catalyzed Stereoselective Synthesis of Spirooxindole Oxazolines. Org. Lett.2011,13,418-421.
© 2004-2018 中国地质图书馆版权所有 京ICP备05064691号 京公网安备11010802017129号 地址：北京市海淀区学院路29号 邮编：100083 电话：办公室：(+86 10)66554848；文献借阅、咨询服务、科技查新：66554700 |