Bronsted酸催化的氮杂-Baylis-Hillman反应
|
摘要
本文首先对近年来氮杂-Baylis-Hillman反应的发展进行了综述,然后,我们对亚胺与丙烯酸甲酯的氮杂-Baylis-Hillman反应进行了研究,分别以非手性的亚磷酸酯和一系列3,3'-位具有较大位阻的联萘骨架的手性膦酸为催化剂对该反应进行了尝试,分别得到了外消旋的和手性的α-亚甲基β-胺基羰基类化合物：
一.以非手性的亚磷酸酯为催化剂,对亚胺与丙烯酸甲酯的氮杂-Baylis-Hillman反应进行了研究,分别对该反应的溶剂、温度、浓度、催化剂、底物进行了筛选,以25-79%的产率得到了外消旋体,为手性膦酸催化的氮杂-Baylis-Hillman反应奠定了基础。
以廉价易得的(R)-BINOL为原料,通过酚氧基保护、Suzuki或Kumada偶联、脱保护,然后在碱性条件下与POCl3反应、水解,合成了一系列3,3'-位具有较大位阻的联萘骨架的手性膦酸；分别用核磁共振氢谱、核磁共振碳谱、质谱,旋光对该系列膦酸进行了表征。
三.以该系列3,3'-位具有较大位阻的联萘骨架的手性膦酸为催化剂尝试对不对称的氮杂-Baylis-Hillman反应进行了研究,分别对该反应体系的溶剂、手性膦酸类催化剂及底物进行了考察,最终,在室温条件下,以1,4-dioxane为溶剂、3,3'-位均为3,5-二甲基苯基取代基的手性膦酸18-DABCO为共催化剂催化的氮杂-Baylis-Hillman反应最高能以80%的产率、31%的对映选择性得到产物。
In this thesis, firstly we viewed the development of aza-Bayllis-Hillman reaction in recent years, then, the aza-Bayllis-Hillman reactions catalyzed by achiral phosphite and chiral phosphoric acid with steric hindrance at 3,3'-position were studied, and the target compoundsα-methylene-β-aminocarbonyl derivatives in the form of racemates and chiral materials were obtained:
1. The aza-Bayllis-Hillman reactions of imines and methyl acrylate catalyzed by achiral phosphite were studied. The reaction conditions, such as solvent, temperature, concentration, catalysts, and substrates were screened. The target aza-Bayllis-Hillman reaction products were obtained with 25-79% yield, which provided the racemates for the chiral phosphoric acid catalyzed aza-Bayllis-Hillman reactions.
2. A series of chiral phosphoric acid with steric hindrance at 3,3'-position were synthesized via multistep transformations from cheap and readily available (R)-BINOL, including pretection of hydroxyl group, Suzuki or Kumada coupling reaction, depretection, reaction with POCl3 under alkaline condition, then hydrolysis. And these chiral phosphoric acids were characterized by 1H-NMR,13C-NMR, MS and [α]D20, respectively.
3. Subsequently, we applied these chiral phosphoric acids to the asymmetric aza-Bayllis-Hillman reactions of imines and methyl acrylate. And different solvents, br(?)nsted acids, substrates were investigated. As a result, the reaction with the solvent of 1,4-dioxane, catalyzed by catalysis 18 was finished with 80% yield and 31% enantioselectivity.
一.以非手性的亚磷酸酯为催化剂,对亚胺与丙烯酸甲酯的氮杂-Baylis-Hillman反应进行了研究,分别对该反应的溶剂、温度、浓度、催化剂、底物进行了筛选,以25-79%的产率得到了外消旋体,为手性膦酸催化的氮杂-Baylis-Hillman反应奠定了基础。
以廉价易得的(R)-BINOL为原料,通过酚氧基保护、Suzuki或Kumada偶联、脱保护,然后在碱性条件下与POCl3反应、水解,合成了一系列3,3'-位具有较大位阻的联萘骨架的手性膦酸；分别用核磁共振氢谱、核磁共振碳谱、质谱,旋光对该系列膦酸进行了表征。
三.以该系列3,3'-位具有较大位阻的联萘骨架的手性膦酸为催化剂尝试对不对称的氮杂-Baylis-Hillman反应进行了研究,分别对该反应体系的溶剂、手性膦酸类催化剂及底物进行了考察,最终,在室温条件下,以1,4-dioxane为溶剂、3,3'-位均为3,5-二甲基苯基取代基的手性膦酸18-DABCO为共催化剂催化的氮杂-Baylis-Hillman反应最高能以80%的产率、31%的对映选择性得到产物。
In this thesis, firstly we viewed the development of aza-Bayllis-Hillman reaction in recent years, then, the aza-Bayllis-Hillman reactions catalyzed by achiral phosphite and chiral phosphoric acid with steric hindrance at 3,3'-position were studied, and the target compoundsα-methylene-β-aminocarbonyl derivatives in the form of racemates and chiral materials were obtained:
1. The aza-Bayllis-Hillman reactions of imines and methyl acrylate catalyzed by achiral phosphite were studied. The reaction conditions, such as solvent, temperature, concentration, catalysts, and substrates were screened. The target aza-Bayllis-Hillman reaction products were obtained with 25-79% yield, which provided the racemates for the chiral phosphoric acid catalyzed aza-Bayllis-Hillman reactions.
2. A series of chiral phosphoric acid with steric hindrance at 3,3'-position were synthesized via multistep transformations from cheap and readily available (R)-BINOL, including pretection of hydroxyl group, Suzuki or Kumada coupling reaction, depretection, reaction with POCl3 under alkaline condition, then hydrolysis. And these chiral phosphoric acids were characterized by 1H-NMR,13C-NMR, MS and [α]D20, respectively.
3. Subsequently, we applied these chiral phosphoric acids to the asymmetric aza-Bayllis-Hillman reactions of imines and methyl acrylate. And different solvents, br(?)nsted acids, substrates were investigated. As a result, the reaction with the solvent of 1,4-dioxane, catalyzed by catalysis 18 was finished with 80% yield and 31% enantioselectivity.
引文
[1]V. Declerck, J. Martinez, F. Lamaty, Aza-Baylis-Hillman Reaction[J]. Chemical Reviews, 2009,109,1-48.
[2]M. Shi, L. H. Chen, C. Q. Li, Chiral Phosphine Lewis Bases Catalyzed Asymmetric aza-Baylis-Hillman Reaction of N-Sulfonated Imines with Activated Olefins[J], J. Am. Chem.Soc.,2005,127,3790.
[3]I. T. Raheem, E. N. Jacobsen, Highly Enantioselective Aza-Baylis-Hillman Reactions Catalyzed by Chiral Thiourea Derivatives [J]. Adv. Synth. Catal.,2005,347,1701-1708.
[4]M. Shi, G. L. Zhao, Aza-Baylis-Hillman Reactions of N-(Arylmethylene)diphen-ylphosphinamides with Activated Olefins in the Presence of Various Lewis Bases[J]. Adv. Synth. Catal.,2004,346,1205-1219.
[5]D. Balan, H. Adolfsson, Selective Formation of a-Methylene-p-amino acid Derivatives through the Aza Version of the Baylis-Hillman Reaction[J]. J. Org. Chem.,2001,66, 6498.
[6]D. Balan, H. Adolfsson, Titanium Isopropoxide as Efficient Catalyst for the aza-Baylis-Hillman Reaction:Selective Formation of a-Methylene-p-amino Acid Deriva-tives[J].J. Org. Chem.,2002,67,2329.
[7]V. Declerck, P. Ribiere, J. Martinez, F. Lamaty, Sequential aza-Baylis-Hillman/Ring Closing Metathesis/Aromatization as a Novel Route for the Synthesis of Substituted Pyrroles[J]. J. Org. Chem.,2004,69,8372.
[8]M. Shi, G. L. Zhao, One-pot aza-Baylis-Hillman reactions of arylaldehydes and diphenylphosphinamide with methyl vinyl ketone in the presence of TiCl4, PPh3, and Et3N[J]. Tetrahedron Lett.,2002,43,9171.
[9]M. Shi, Y. M. Xu, Diastereoselective Baylis-Hillman type reactions of chiral non-racemic N-sulfinimines with cyclopent-2-en-l-one[J]. Tetrahedron:Asymmetry,2002,13,1195.
[10]V. K. Aggarwal, A. M. M. Castro, A. Mereu, H. Adams, The use of enantiomerically pure N-sulfinimines in asymmetric Baylis-Hillman reactions[J]. Tetrahedron Lett.,2002,43, 1577-1581.
[11]A. Kamimura, Y. Gunjigake, H. Mitsuder, S. Yokoyama, A Facile Preparation of tt-Hy-drazinoet,15-unsaturated Ketones via Aza-Baylis-Hillman Reaction[J]. Tetrahedron Lett., 1998,39,7323.
[12]Y. M. Xu, M. Shi, Highly Efficient aza-Baylis-Hillman Reaction of N-Tosylated Imines with MVK, Acrolein, and Phenyl Acrylate or α-Naphthyl Acrylate:Lewis Base Effects and A Convenient Method to Synthesize α, β-Unsaturated β-Amino Carbonyl Com-pounds[J]. J. Org. Chem.,2004,69,417-425.
[13]Y. L. Shi, Y. M. Xu, M. Shi, Aza-Baylis-Hillman Reaction of β-Substituted Activated Olefins with N-Tosyl Imines[J]. Adv. Synth. Catal.,2004,346,1220-1230.
[14]G. L. Zhao, J. W. Huang, M. Shi, Abnormal Aza-Baylis-Hillman Reaction of N-Tosylated Imines with Ethyl 2,3-Butadienoate and Penta-3,4-dien-2-one[J]. Org. Lett.,2003,5, 4737-4739.
[15]X. Mi, S. Luo, H. Xu, L. Zhang, J. P. Cheng, Hydroxyl ionic liquid (HIL)-immobilized quinuclidine for Baylis-Hillman catalysis:synergistic effect of ionic liquids as organocatalyst supports[J]. Tetrahedron,2006,62,2537.
[16]P. Ribie're, N. Y. Bhatnagar, J. Martinez, F. Lamaty, Direct Access to Functionalized Cyclic Enones Using Mannich, Morita-Baylis-Hillman and Elimination Reactions[J]. QSAR Comb. Sci.,2004,23,911.
[17]P. Buskens, J. Klankermayer, W. Leitner, Bifunctional Activation and Racemization in the Catalytic Asymmetric Aza-Baylis-Hillman Reaction[J]. J. Am. Chem. Soc.,2005,127, 16762.
[18]A. B. Baylis, M. E. D. Hillman, A Facile Zn-mediated Stereoselective Synthesis of (E)-and (Z)-Trisubstituted Alkenes from Baylis-Hillman Adducts in Water and Its Application[J]. Chem. Abstr.,1972,77,34174.
[19]K. i. Morita, Z. Suzuki, H. Hirose, Lithium perchlorate-accelerated Baylis-Hillman reactions[J]. Bull. Chem. Soc. Jpn.,1968,41,2815.
[20]J. W. Huang, M. Shi, Polymer-Supported Lewis Bases for the Baylis-Hillman Reaction [3]. Adv. Synth. Catal.,2003,345,953-958.
[21]A. B Baylis, M. E. D. Hillman, Acrylic compounds[M]. Chem. Abstr.,1972,77,34174.
[22]P. Perlmutter, C. C. Teo, A simple synthesis of 2-methylidene-3-aminopropanoates[J]. Tetrahedron Lett.,1984,25,5951.
[23]S. Bertenshaw, M. Kahn, Phosphine mediated synthesis of 2-methylidene-3-aminoesters and ketones[J]. Tetrahedron Lett.,1989,30,2731.
[24]D. Balan, H. Adolfsson, Titanium Isopropoxide as Efficient Catalyst for the Aza-Baylis-Hillman Reaction. Selective Formation of α-Methylene-β-amino Acid Derivatives[J]. J. Org. Chem.,2002,67,2329.
[25]M.Shi, G. L.Zhao, One-pot aza-Baylis-Hillman reactions of arylaldehydes and Diphenylphosphinamide with methyl vinyl ketone in the presence of TiCl4, PPh3, and Et3N[J]. Tetrahedron Lett.,2002,43,9171.
[26]V. K. Aggarwal, A. M. M. Castro, A. Mereu, H. Adams, The use of enantiomerically pure N-sulfinimines in asymmetric Baylis-Hillman reactions[J]. Tetrahedron Lett.,2002,43, 1577.
[27]M. Shi, Y. M. Xu, Lewis base effects in the Baylis-Hillman reaction of imines with cyclohex-2-en-l-one and cyclopent-2-en-l-one[J]. Chem. Commun.,2001,1876.
[28]L. He, T. Y. Jian, S. Ye, N-Heterocyclic Carbene Catalyzed Aza-Morita-Baylis-Hillman Reaction of Cyclic Enones with N-Tosylarylimines[J]. J. Org. Chem.,2007,72, 7466.
[29]Z. Wu, G. Zhou, J. Zhou, W. Guo, Aza-Baylis-Hillman Reaction of N-Tosylated Imines with Acrylamide or N-Arylacrylamide. Synth. Commun.,2006,36,2491-2502.
[30]M. Takagi, K. Yamamoto, Carbamate-derected stereoselective hydrogenation and kinetic resolution of N-protected a-(a-aminoalkyl) acrylates[J]. Tetrahedron,1991,47, 8869.
[31]N. Sergeeva, A. S. Golubev, K. Burger, Synthesis of Partially Fluorinated b-Amino Acids via Morita-Baylis-Hillman Reaction[J]. Synthesis,2001,281-285.
[32]Y. M. Xu, M. Shi, Highly Efficient aza-Baylis-Hillman Reaction of N-Tosylated Imines with MVK, Acrolein, and Phenyl Acrylate or a-Naphthyl Acrylate:Lewis Base Effects and A Convenient Method to Synthesize α,β-Unsaturated β-Amino Carbonyl Compounds[J]. J. Org. Chem.,2004,69,417.
[33]V. Declerck, H. Allouchi, J. Martinez, F. Lamaty,2-Trimethylsilylethanesulfonyl (SES) versus Tosyl (Ts) Protecting Group in the Preparation of Nitrogen-Containing Five-Membered Rings. A Novel Route for the Synthesis of Substituted Pyrrolines and Pyrrolidines[J]. J. Org. Chem.,2007,72,1518.
[34]M. Kim, K. Y. Lee, S. Lee, J. N. Kim, Ring-closing metathesis toward the synthesis of 2,5-dihydrofuran and 2,5-dihydropyrrole skeletons from Baylis-Hillman adducts[J]. Tetrahedron Lett.,2004,45,2805-2808.
[35]S. Gowrisankar, H. S. Kim, H. S. Lee, J. N. Kim, An Expeditious Synthesis of Substituted Pyrrolidines and Tetrahydrofurans Starting from Baylis-Hillman Adducts[J]. Bull. Korean Chem. Soc.,2007,28,1844.
[36]S. Gowrisankar, K. Y. Lee, J. N. Kim, Synthesis of 3,4-disubstituted 2,5-dihydrofurans starting from the Baylis-Hillman adducts via consecutive radical cyclization, halolactonization, and decarboxylation strategy[J]. Tetrahedron Lett.,2005,46,4859.
[37]D. Y. Park, M. J. Lee, T. H. Kim, J. N. Kim, Regioselective construction of polysubstituted pyridine ring from Baylis-Hillman adducts via sequential introduction of tosylamide, Michael reaction, aldol condensation, and elimination of TsH[J]. Tetrahedron Lett.,2005,46,8799-8803.
[38]J. M. Sorbetti, K. N. Clary, D. A. Rankic, J. E. Wulff, M. Parvez, T. G. Back, Aza-Morita-Baylis-Hillman Reactions and Cyclizations of Conjugated Dienes Activated by Sulfone, Ester, and Keto Groups[J]. J. Org. Chem.,2007,72,3326.
[39]J. N. Kim, H. J. Lee, K. Y. Lee, H. S. Kim, Synthesis of 3-quinolinecarboxylic acid esters from the Baylis-Hillman adducts of 2-halobenzaldehyde N-tosylimines[J]. Tetrahedron Lett.,2001,42,3737-3740.
[40]J. N. Kim, H. S. Kim, J. H. Gong, Y. M. Chung, Synthesis of N-substituted 1,4-dihydroquinolines from the Baylis-Hillman acetates via the successive SN2-SNar isomerization strategy[J]. Tetrahedron Lett.,2001,42,8341-8344.
[41]S. Nag, G. P. Yadav, P. R. Maulik, S. Batra, Sodium hydride mediated cascade reaction towards the synthesis of 1,5-disubstituted uracil from cyanamides derived from Baylis-Hillman adducts[J]. Synthesis,2007,911.
[42]V. K. Aggarwal, A. M. M. Castro, A. Mereu, H. Adams, The use of enantiomerically pure N-sulfinimines in asymmetric Baylis-Hillman reactions[J]. Tetrahedron Lett.,2002,43, 1577.
[43]T. C. Wabnitz, J. B. Spencer, A General Br(?)nsted Acid-Catalyzed Hetero-Michael Addition of Nitrogen, Oxygen, and Sulfur Nucleophiles[J]. Org. Lett.,2003 2141-2144.
[44]J. W. Sun, S. A. Kozmin, Br(?)nsted Acid-Promoted Cyclizations of 1-Siloxy-1,5-diynes [J]. J. Am. Chem. Soc.,2005,127,13512-13513.
[45]Z. g. Li, J.l. Zhang, C. Brouwer, C. G. Yang, N. W. Reich, C. He, A Convenient FeCl3-Catalyzed Hydroarylation of Styrenes[J]. Org. Lett.,2006,8,19.
[46]S. C. Pan, B. List, The Catalytic Acylcyanation of Imines[J]. Chem, Asian J.,2008,3,430-437.
[47]D. Basavaiah, P. DharmaRao, R. S. Hyma, The Baylis-Hillman reaction:A novel carbon-carbon bond forming reaction[J]. Tetrahedron,1996,52,8001.
[48]M. Shi, Y. M. Xu, Diastereoselective Baylis-Hillman type reactions of chiral non-racemic N-sulfinimines with cyclopent-2-en-1-one[J]. Tetrahedron:Asymmetry,2002, 13,1195-1200.
[49]F. A. Davis, Y. Zhang, T. Fang, D. L. Fanelli, H. Zhang, Improved Synthesis of Enantiopure Sulfinimines (Thiooxime S-Oxides) from p-Toluenesulfinamide and Aldehydes and Ketones[J]. J. Org. Chem.,1999,64,1403.
[50]S. Kawahara, A. Nakano, T. Esumi, Y. Iwabuchi, S. Hatakeyama, β-Isocupreidine-Catalyzed Asymmetric Baylis-Hillman Reaction of Imines[J]. Org. Lett.,2003,5, 3103-3105.
[51]K. Matsui, S. Takizawa, H. Sasai, Bifunctional Organocatalysts for Enantioselective aza-Morita-Baylis-Hillman Reaction[J]. J. Am. Chem. Soc.,2005,127,3680-3681.
[52]M. Shi, L. H. Chen, C. Q. Li, Chiral Phosphine Lewis Bases Catalyzed Asymmetric aza-Baylis-Hillman Reaction of N-Sulfonated Imines with Activated Olefins[J]. J. Am. Chem. Soc.,2005,127,3790-3800.
[53]Y. H. Liu, L. Chen, H. M. Shi, Asymmetric Aza-Morita-Baylis-Hillman Reaction of N-Sulfonated Imines with Activated Olefins Catalyzed by Chiral Phosphine Lewis Bases Bearing Multiple Phenol Groups[J]. Adv. Synth. Catal.,2006,348,973-979.
[54]I. T. Raheem, E. N. Jacobsen, Highly Enantioselective Aza-Baylis—Hillman Reactions Catalyzed by Chiral Thiourea Derivatives[J]. Adv. Synth. Catal.,2005,347,1701-1708.
[55]S. C. ihalova, M. Remes, I. Cisarova, J. Vesely, Highly Enantioselective Aza-Baylis-Hillman-Type Reaction of α,β-Unsaturated Aldehydes with In Situ Generated N-Boc-and N-Cbz-Imines[J]. Eur. J. Org. Chem.,2009,6277-6280.
[56]G. Gottarelli, G. P. Spada, Spontaneous resolution of 2,2'-dimethoxy-1,1'-binaphthale-ne[J]. J. Org. Chem.,1991,56,2096-2098.
[57]D. J. Bayston, J. L. Fraser, M. R. Ashton, A. D. Baxter, M. E. C. Polywka, E. Moses, Preparation and Use of a Polymer Supported BINAP Hydrogenation Catalyst[J]. J. Org. Chem.,1998,63,3137-3140.
[58]P. Wipf, J. K. Jung, Formal total synthsis of (+)-diepoxin[J]. J. Org. Chem.,2000,65, 6319-6337.
[59]S. S. Zhu, D. R. Cefalo, D. S. La, J. Y. Jamieson, W. M. Davis, A. H. Hoveyda, R. R. Schrock, Chiral Mo-Binol Complexes:Activity, Synthesis, and Structure. Efficient Enantioselective Six-Membered Ring Synthesis through Catalytic Metathesis[J]. J. Am. Chem. Soc.,1999,121,8251-8259.
[60]T. Ooi, M. Kameda, K. Maruoka, Asymmetric Allylboration of Aldehydes and Ketones Using 3,3'-Disubstitutedbinaphthol-Modified Boronates[J]. Org. Lett.,2004,6, 2701-2704.
[61]T. Ooi, M. Kameda, K. j. Maruoka, Design of N-Spiro C2-Symmetric Chiral Quaternary Ammonium Bromides as Novel Chiral Phase-Transfer Catalysts:Synthesis and Application to Practical Asymmetric Synthesis of a-Amino Acids [J]. J. Am. Chem. Soc., 2003,125,5139-5151.
[62]A. Bahr, A. S. Droz, M. Piintener, U. Neidlein, S. Anderson, P. Seiler, F.Diederich, Molecular recognition of pyranosides by a family of trimeric,1,1′-binaphthalene-derived cyclophane receptors[J]. Helv. Chim. Acta,1998,81,1931-1963.
[63]K. B. Simonsen, K. T. Gothelf, K. A. J(?)rgensen, A Simple Synthetic Approach to 3,3'-Diaryl BINOLS[J]. J. Org. Chem.,1998,63,7536-7538.
[64]T. Dron, A. C. Chamayou, C. Janiak, Hydrophilic interior between hydrophobic regions in inverse bilayer structures of cation-1,1'-binaphthalene-2,2'-diyl phosphate salts[J]. New.J. Chem.,2006,30,156-167.
[65]K. Tamao, K. Sumitani, Y. Kiso, M. Zembayashi, A. Fujioka, S. i. Kodama, I. Nakajima, A. Minato, M, Kumada, Nickel-Phosphine Complex-Catalyzed Grignard Coupling. I. Cross-Coupling of Alkyl, Aryl, and Alkenyl Grignard Reagents with Aryl and Alkenyl Halides:General Scope and Limitations[J]. Bulletin of the Chemical Society of Japan, 1976,49,1958-1969.
[66]P. Wipf, J. K. Jung, Formal total Synthesis of (+)-Diepoxin[J]. J. Org. Chem.,2000,65, 6319-6337.
[67]D. Uraguchi, M. Terada, Chiral Br(?)nsted Acid-Catalyzed Direct Mannich Reactions via Electrophilic Activation [J]. J. Am. Chem. Soc.,2004,126,5356-5357.
[68]F. Yang, D. Zhao, J. Lan, P. Xi, Y. Li, S. Xiang, J. You, Self-Assembled Bifunctional Catalysis Induced by Metal Coordination Interactions:An Exceptionally Efficient Approach to Enantioselective Hydrophosphonylation[J], Angew. Chem. Int. Ed.,2008, 47,5646-5649.
[69]T. R. Wu, L. x. Shen, J. M. Chong, Asymmetric allylboration of Aldehydes and Ketones Using 3,3'-Disubstituted Binaphthol-Modified Boronates[J]. Org. Lett.,2004,6, 2710-2704.
[70]Q. Wang, X. Chen, L. Tao, L. Wang, D. Xiao, X. Q. Yu, L. Pu, Enantioselective-Fluorescent Recognition of Amino Alcohols by a Chiral Tetrahydroxyl 1,1'-Bina-phthyl Compound[J].J. Org. Chem.,2007,72,97-101.
[71]S. Matsunaga, J. Das, J. Roels, E. M. Vogl, N. Yamamoto, T. Iida, K. Yamaguchi, M. Shibasaki, Catalytic Enantioselective meso-Epoxide Ring Opening Reaction with Phenolic Oxygen Nucleophile Promoted by Gallium Heterobimetallic Multifunctional Complexes[J].J. Am. Chem. Soc.,2000,122,2252-2260.
[72]X. H. Chen, W. Q. Zhang, L. Z. Gong, Asymmetric Organocatalytic Three-Component 1,3-Dipolar Cycloaddition:Control of Stereochemistry via a Chiral Br(?)nsted Acid Activated Dipole[J]. J. Am. Chem. Soc.,2008,130,5652-5653.
[73]M. Shi, Y. M. Xu, Y. L. Shi, Catalytic, Asymmetric Aza-Baylis-Hillman Reaction of N-Sulfonated Imines with Activated Olefins by Quinidine-Derived Chiral Amines[J]. Chem. Eur. J.,2005,11,1794-1802.
[74]X. Huang, J.1. Huang, Y. h. Wen, X. m. Feng, Asymmetric Strecker Reaction of Ketoimines Catalyzed by a Novel Chiral Bifunctional N,N′-Dioxide[J]. Adv. Synth. Catal.,2006,348,2579-2584.
[75]N. Baricordi, S. Benetti, G. Biondini, C. D. Risi, G. P. Pollini, A new"one-pot" synthesis of 2-substituted 3-nitropyrrolidines through a multicomponent domino reaction[J]. Tetrahedron Lett.,2004,45,1373-1375.
[76]T. Ooi, M. Kameda, K. Maruoka, Design of N-Spiro C2-Symmetric Chiral Quaternary Ammonium Bromides as Novel Chiral Phase-Transfer Catalysts:Synthesis and Application to Practical Asymmetric Synthesis of a-Amino Acids[J]. J. Am. Chem. Soc., 2003,125,5139-5151.
[2]M. Shi, L. H. Chen, C. Q. Li, Chiral Phosphine Lewis Bases Catalyzed Asymmetric aza-Baylis-Hillman Reaction of N-Sulfonated Imines with Activated Olefins[J], J. Am. Chem.Soc.,2005,127,3790.
[3]I. T. Raheem, E. N. Jacobsen, Highly Enantioselective Aza-Baylis-Hillman Reactions Catalyzed by Chiral Thiourea Derivatives [J]. Adv. Synth. Catal.,2005,347,1701-1708.
[4]M. Shi, G. L. Zhao, Aza-Baylis-Hillman Reactions of N-(Arylmethylene)diphen-ylphosphinamides with Activated Olefins in the Presence of Various Lewis Bases[J]. Adv. Synth. Catal.,2004,346,1205-1219.
[5]D. Balan, H. Adolfsson, Selective Formation of a-Methylene-p-amino acid Derivatives through the Aza Version of the Baylis-Hillman Reaction[J]. J. Org. Chem.,2001,66, 6498.
[6]D. Balan, H. Adolfsson, Titanium Isopropoxide as Efficient Catalyst for the aza-Baylis-Hillman Reaction:Selective Formation of a-Methylene-p-amino Acid Deriva-tives[J].J. Org. Chem.,2002,67,2329.
[7]V. Declerck, P. Ribiere, J. Martinez, F. Lamaty, Sequential aza-Baylis-Hillman/Ring Closing Metathesis/Aromatization as a Novel Route for the Synthesis of Substituted Pyrroles[J]. J. Org. Chem.,2004,69,8372.
[8]M. Shi, G. L. Zhao, One-pot aza-Baylis-Hillman reactions of arylaldehydes and diphenylphosphinamide with methyl vinyl ketone in the presence of TiCl4, PPh3, and Et3N[J]. Tetrahedron Lett.,2002,43,9171.
[9]M. Shi, Y. M. Xu, Diastereoselective Baylis-Hillman type reactions of chiral non-racemic N-sulfinimines with cyclopent-2-en-l-one[J]. Tetrahedron:Asymmetry,2002,13,1195.
[10]V. K. Aggarwal, A. M. M. Castro, A. Mereu, H. Adams, The use of enantiomerically pure N-sulfinimines in asymmetric Baylis-Hillman reactions[J]. Tetrahedron Lett.,2002,43, 1577-1581.
[11]A. Kamimura, Y. Gunjigake, H. Mitsuder, S. Yokoyama, A Facile Preparation of tt-Hy-drazinoet,15-unsaturated Ketones via Aza-Baylis-Hillman Reaction[J]. Tetrahedron Lett., 1998,39,7323.
[12]Y. M. Xu, M. Shi, Highly Efficient aza-Baylis-Hillman Reaction of N-Tosylated Imines with MVK, Acrolein, and Phenyl Acrylate or α-Naphthyl Acrylate:Lewis Base Effects and A Convenient Method to Synthesize α, β-Unsaturated β-Amino Carbonyl Com-pounds[J]. J. Org. Chem.,2004,69,417-425.
[13]Y. L. Shi, Y. M. Xu, M. Shi, Aza-Baylis-Hillman Reaction of β-Substituted Activated Olefins with N-Tosyl Imines[J]. Adv. Synth. Catal.,2004,346,1220-1230.
[14]G. L. Zhao, J. W. Huang, M. Shi, Abnormal Aza-Baylis-Hillman Reaction of N-Tosylated Imines with Ethyl 2,3-Butadienoate and Penta-3,4-dien-2-one[J]. Org. Lett.,2003,5, 4737-4739.
[15]X. Mi, S. Luo, H. Xu, L. Zhang, J. P. Cheng, Hydroxyl ionic liquid (HIL)-immobilized quinuclidine for Baylis-Hillman catalysis:synergistic effect of ionic liquids as organocatalyst supports[J]. Tetrahedron,2006,62,2537.
[16]P. Ribie're, N. Y. Bhatnagar, J. Martinez, F. Lamaty, Direct Access to Functionalized Cyclic Enones Using Mannich, Morita-Baylis-Hillman and Elimination Reactions[J]. QSAR Comb. Sci.,2004,23,911.
[17]P. Buskens, J. Klankermayer, W. Leitner, Bifunctional Activation and Racemization in the Catalytic Asymmetric Aza-Baylis-Hillman Reaction[J]. J. Am. Chem. Soc.,2005,127, 16762.
[18]A. B. Baylis, M. E. D. Hillman, A Facile Zn-mediated Stereoselective Synthesis of (E)-and (Z)-Trisubstituted Alkenes from Baylis-Hillman Adducts in Water and Its Application[J]. Chem. Abstr.,1972,77,34174.
[19]K. i. Morita, Z. Suzuki, H. Hirose, Lithium perchlorate-accelerated Baylis-Hillman reactions[J]. Bull. Chem. Soc. Jpn.,1968,41,2815.
[20]J. W. Huang, M. Shi, Polymer-Supported Lewis Bases for the Baylis-Hillman Reaction [3]. Adv. Synth. Catal.,2003,345,953-958.
[21]A. B Baylis, M. E. D. Hillman, Acrylic compounds[M]. Chem. Abstr.,1972,77,34174.
[22]P. Perlmutter, C. C. Teo, A simple synthesis of 2-methylidene-3-aminopropanoates[J]. Tetrahedron Lett.,1984,25,5951.
[23]S. Bertenshaw, M. Kahn, Phosphine mediated synthesis of 2-methylidene-3-aminoesters and ketones[J]. Tetrahedron Lett.,1989,30,2731.
[24]D. Balan, H. Adolfsson, Titanium Isopropoxide as Efficient Catalyst for the Aza-Baylis-Hillman Reaction. Selective Formation of α-Methylene-β-amino Acid Derivatives[J]. J. Org. Chem.,2002,67,2329.
[25]M.Shi, G. L.Zhao, One-pot aza-Baylis-Hillman reactions of arylaldehydes and Diphenylphosphinamide with methyl vinyl ketone in the presence of TiCl4, PPh3, and Et3N[J]. Tetrahedron Lett.,2002,43,9171.
[26]V. K. Aggarwal, A. M. M. Castro, A. Mereu, H. Adams, The use of enantiomerically pure N-sulfinimines in asymmetric Baylis-Hillman reactions[J]. Tetrahedron Lett.,2002,43, 1577.
[27]M. Shi, Y. M. Xu, Lewis base effects in the Baylis-Hillman reaction of imines with cyclohex-2-en-l-one and cyclopent-2-en-l-one[J]. Chem. Commun.,2001,1876.
[28]L. He, T. Y. Jian, S. Ye, N-Heterocyclic Carbene Catalyzed Aza-Morita-Baylis-Hillman Reaction of Cyclic Enones with N-Tosylarylimines[J]. J. Org. Chem.,2007,72, 7466.
[29]Z. Wu, G. Zhou, J. Zhou, W. Guo, Aza-Baylis-Hillman Reaction of N-Tosylated Imines with Acrylamide or N-Arylacrylamide. Synth. Commun.,2006,36,2491-2502.
[30]M. Takagi, K. Yamamoto, Carbamate-derected stereoselective hydrogenation and kinetic resolution of N-protected a-(a-aminoalkyl) acrylates[J]. Tetrahedron,1991,47, 8869.
[31]N. Sergeeva, A. S. Golubev, K. Burger, Synthesis of Partially Fluorinated b-Amino Acids via Morita-Baylis-Hillman Reaction[J]. Synthesis,2001,281-285.
[32]Y. M. Xu, M. Shi, Highly Efficient aza-Baylis-Hillman Reaction of N-Tosylated Imines with MVK, Acrolein, and Phenyl Acrylate or a-Naphthyl Acrylate:Lewis Base Effects and A Convenient Method to Synthesize α,β-Unsaturated β-Amino Carbonyl Compounds[J]. J. Org. Chem.,2004,69,417.
[33]V. Declerck, H. Allouchi, J. Martinez, F. Lamaty,2-Trimethylsilylethanesulfonyl (SES) versus Tosyl (Ts) Protecting Group in the Preparation of Nitrogen-Containing Five-Membered Rings. A Novel Route for the Synthesis of Substituted Pyrrolines and Pyrrolidines[J]. J. Org. Chem.,2007,72,1518.
[34]M. Kim, K. Y. Lee, S. Lee, J. N. Kim, Ring-closing metathesis toward the synthesis of 2,5-dihydrofuran and 2,5-dihydropyrrole skeletons from Baylis-Hillman adducts[J]. Tetrahedron Lett.,2004,45,2805-2808.
[35]S. Gowrisankar, H. S. Kim, H. S. Lee, J. N. Kim, An Expeditious Synthesis of Substituted Pyrrolidines and Tetrahydrofurans Starting from Baylis-Hillman Adducts[J]. Bull. Korean Chem. Soc.,2007,28,1844.
[36]S. Gowrisankar, K. Y. Lee, J. N. Kim, Synthesis of 3,4-disubstituted 2,5-dihydrofurans starting from the Baylis-Hillman adducts via consecutive radical cyclization, halolactonization, and decarboxylation strategy[J]. Tetrahedron Lett.,2005,46,4859.
[37]D. Y. Park, M. J. Lee, T. H. Kim, J. N. Kim, Regioselective construction of polysubstituted pyridine ring from Baylis-Hillman adducts via sequential introduction of tosylamide, Michael reaction, aldol condensation, and elimination of TsH[J]. Tetrahedron Lett.,2005,46,8799-8803.
[38]J. M. Sorbetti, K. N. Clary, D. A. Rankic, J. E. Wulff, M. Parvez, T. G. Back, Aza-Morita-Baylis-Hillman Reactions and Cyclizations of Conjugated Dienes Activated by Sulfone, Ester, and Keto Groups[J]. J. Org. Chem.,2007,72,3326.
[39]J. N. Kim, H. J. Lee, K. Y. Lee, H. S. Kim, Synthesis of 3-quinolinecarboxylic acid esters from the Baylis-Hillman adducts of 2-halobenzaldehyde N-tosylimines[J]. Tetrahedron Lett.,2001,42,3737-3740.
[40]J. N. Kim, H. S. Kim, J. H. Gong, Y. M. Chung, Synthesis of N-substituted 1,4-dihydroquinolines from the Baylis-Hillman acetates via the successive SN2-SNar isomerization strategy[J]. Tetrahedron Lett.,2001,42,8341-8344.
[41]S. Nag, G. P. Yadav, P. R. Maulik, S. Batra, Sodium hydride mediated cascade reaction towards the synthesis of 1,5-disubstituted uracil from cyanamides derived from Baylis-Hillman adducts[J]. Synthesis,2007,911.
[42]V. K. Aggarwal, A. M. M. Castro, A. Mereu, H. Adams, The use of enantiomerically pure N-sulfinimines in asymmetric Baylis-Hillman reactions[J]. Tetrahedron Lett.,2002,43, 1577.
[43]T. C. Wabnitz, J. B. Spencer, A General Br(?)nsted Acid-Catalyzed Hetero-Michael Addition of Nitrogen, Oxygen, and Sulfur Nucleophiles[J]. Org. Lett.,2003 2141-2144.
[44]J. W. Sun, S. A. Kozmin, Br(?)nsted Acid-Promoted Cyclizations of 1-Siloxy-1,5-diynes [J]. J. Am. Chem. Soc.,2005,127,13512-13513.
[45]Z. g. Li, J.l. Zhang, C. Brouwer, C. G. Yang, N. W. Reich, C. He, A Convenient FeCl3-Catalyzed Hydroarylation of Styrenes[J]. Org. Lett.,2006,8,19.
[46]S. C. Pan, B. List, The Catalytic Acylcyanation of Imines[J]. Chem, Asian J.,2008,3,430-437.
[47]D. Basavaiah, P. DharmaRao, R. S. Hyma, The Baylis-Hillman reaction:A novel carbon-carbon bond forming reaction[J]. Tetrahedron,1996,52,8001.
[48]M. Shi, Y. M. Xu, Diastereoselective Baylis-Hillman type reactions of chiral non-racemic N-sulfinimines with cyclopent-2-en-1-one[J]. Tetrahedron:Asymmetry,2002, 13,1195-1200.
[49]F. A. Davis, Y. Zhang, T. Fang, D. L. Fanelli, H. Zhang, Improved Synthesis of Enantiopure Sulfinimines (Thiooxime S-Oxides) from p-Toluenesulfinamide and Aldehydes and Ketones[J]. J. Org. Chem.,1999,64,1403.
[50]S. Kawahara, A. Nakano, T. Esumi, Y. Iwabuchi, S. Hatakeyama, β-Isocupreidine-Catalyzed Asymmetric Baylis-Hillman Reaction of Imines[J]. Org. Lett.,2003,5, 3103-3105.
[51]K. Matsui, S. Takizawa, H. Sasai, Bifunctional Organocatalysts for Enantioselective aza-Morita-Baylis-Hillman Reaction[J]. J. Am. Chem. Soc.,2005,127,3680-3681.
[52]M. Shi, L. H. Chen, C. Q. Li, Chiral Phosphine Lewis Bases Catalyzed Asymmetric aza-Baylis-Hillman Reaction of N-Sulfonated Imines with Activated Olefins[J]. J. Am. Chem. Soc.,2005,127,3790-3800.
[53]Y. H. Liu, L. Chen, H. M. Shi, Asymmetric Aza-Morita-Baylis-Hillman Reaction of N-Sulfonated Imines with Activated Olefins Catalyzed by Chiral Phosphine Lewis Bases Bearing Multiple Phenol Groups[J]. Adv. Synth. Catal.,2006,348,973-979.
[54]I. T. Raheem, E. N. Jacobsen, Highly Enantioselective Aza-Baylis—Hillman Reactions Catalyzed by Chiral Thiourea Derivatives[J]. Adv. Synth. Catal.,2005,347,1701-1708.
[55]S. C. ihalova, M. Remes, I. Cisarova, J. Vesely, Highly Enantioselective Aza-Baylis-Hillman-Type Reaction of α,β-Unsaturated Aldehydes with In Situ Generated N-Boc-and N-Cbz-Imines[J]. Eur. J. Org. Chem.,2009,6277-6280.
[56]G. Gottarelli, G. P. Spada, Spontaneous resolution of 2,2'-dimethoxy-1,1'-binaphthale-ne[J]. J. Org. Chem.,1991,56,2096-2098.
[57]D. J. Bayston, J. L. Fraser, M. R. Ashton, A. D. Baxter, M. E. C. Polywka, E. Moses, Preparation and Use of a Polymer Supported BINAP Hydrogenation Catalyst[J]. J. Org. Chem.,1998,63,3137-3140.
[58]P. Wipf, J. K. Jung, Formal total synthsis of (+)-diepoxin[J]. J. Org. Chem.,2000,65, 6319-6337.
[59]S. S. Zhu, D. R. Cefalo, D. S. La, J. Y. Jamieson, W. M. Davis, A. H. Hoveyda, R. R. Schrock, Chiral Mo-Binol Complexes:Activity, Synthesis, and Structure. Efficient Enantioselective Six-Membered Ring Synthesis through Catalytic Metathesis[J]. J. Am. Chem. Soc.,1999,121,8251-8259.
[60]T. Ooi, M. Kameda, K. Maruoka, Asymmetric Allylboration of Aldehydes and Ketones Using 3,3'-Disubstitutedbinaphthol-Modified Boronates[J]. Org. Lett.,2004,6, 2701-2704.
[61]T. Ooi, M. Kameda, K. j. Maruoka, Design of N-Spiro C2-Symmetric Chiral Quaternary Ammonium Bromides as Novel Chiral Phase-Transfer Catalysts:Synthesis and Application to Practical Asymmetric Synthesis of a-Amino Acids [J]. J. Am. Chem. Soc., 2003,125,5139-5151.
[62]A. Bahr, A. S. Droz, M. Piintener, U. Neidlein, S. Anderson, P. Seiler, F.Diederich, Molecular recognition of pyranosides by a family of trimeric,1,1′-binaphthalene-derived cyclophane receptors[J]. Helv. Chim. Acta,1998,81,1931-1963.
[63]K. B. Simonsen, K. T. Gothelf, K. A. J(?)rgensen, A Simple Synthetic Approach to 3,3'-Diaryl BINOLS[J]. J. Org. Chem.,1998,63,7536-7538.
[64]T. Dron, A. C. Chamayou, C. Janiak, Hydrophilic interior between hydrophobic regions in inverse bilayer structures of cation-1,1'-binaphthalene-2,2'-diyl phosphate salts[J]. New.J. Chem.,2006,30,156-167.
[65]K. Tamao, K. Sumitani, Y. Kiso, M. Zembayashi, A. Fujioka, S. i. Kodama, I. Nakajima, A. Minato, M, Kumada, Nickel-Phosphine Complex-Catalyzed Grignard Coupling. I. Cross-Coupling of Alkyl, Aryl, and Alkenyl Grignard Reagents with Aryl and Alkenyl Halides:General Scope and Limitations[J]. Bulletin of the Chemical Society of Japan, 1976,49,1958-1969.
[66]P. Wipf, J. K. Jung, Formal total Synthesis of (+)-Diepoxin[J]. J. Org. Chem.,2000,65, 6319-6337.
[67]D. Uraguchi, M. Terada, Chiral Br(?)nsted Acid-Catalyzed Direct Mannich Reactions via Electrophilic Activation [J]. J. Am. Chem. Soc.,2004,126,5356-5357.
[68]F. Yang, D. Zhao, J. Lan, P. Xi, Y. Li, S. Xiang, J. You, Self-Assembled Bifunctional Catalysis Induced by Metal Coordination Interactions:An Exceptionally Efficient Approach to Enantioselective Hydrophosphonylation[J], Angew. Chem. Int. Ed.,2008, 47,5646-5649.
[69]T. R. Wu, L. x. Shen, J. M. Chong, Asymmetric allylboration of Aldehydes and Ketones Using 3,3'-Disubstituted Binaphthol-Modified Boronates[J]. Org. Lett.,2004,6, 2710-2704.
[70]Q. Wang, X. Chen, L. Tao, L. Wang, D. Xiao, X. Q. Yu, L. Pu, Enantioselective-Fluorescent Recognition of Amino Alcohols by a Chiral Tetrahydroxyl 1,1'-Bina-phthyl Compound[J].J. Org. Chem.,2007,72,97-101.
[71]S. Matsunaga, J. Das, J. Roels, E. M. Vogl, N. Yamamoto, T. Iida, K. Yamaguchi, M. Shibasaki, Catalytic Enantioselective meso-Epoxide Ring Opening Reaction with Phenolic Oxygen Nucleophile Promoted by Gallium Heterobimetallic Multifunctional Complexes[J].J. Am. Chem. Soc.,2000,122,2252-2260.
[72]X. H. Chen, W. Q. Zhang, L. Z. Gong, Asymmetric Organocatalytic Three-Component 1,3-Dipolar Cycloaddition:Control of Stereochemistry via a Chiral Br(?)nsted Acid Activated Dipole[J]. J. Am. Chem. Soc.,2008,130,5652-5653.
[73]M. Shi, Y. M. Xu, Y. L. Shi, Catalytic, Asymmetric Aza-Baylis-Hillman Reaction of N-Sulfonated Imines with Activated Olefins by Quinidine-Derived Chiral Amines[J]. Chem. Eur. J.,2005,11,1794-1802.
[74]X. Huang, J.1. Huang, Y. h. Wen, X. m. Feng, Asymmetric Strecker Reaction of Ketoimines Catalyzed by a Novel Chiral Bifunctional N,N′-Dioxide[J]. Adv. Synth. Catal.,2006,348,2579-2584.
[75]N. Baricordi, S. Benetti, G. Biondini, C. D. Risi, G. P. Pollini, A new"one-pot" synthesis of 2-substituted 3-nitropyrrolidines through a multicomponent domino reaction[J]. Tetrahedron Lett.,2004,45,1373-1375.
[76]T. Ooi, M. Kameda, K. Maruoka, Design of N-Spiro C2-Symmetric Chiral Quaternary Ammonium Bromides as Novel Chiral Phase-Transfer Catalysts:Synthesis and Application to Practical Asymmetric Synthesis of a-Amino Acids[J]. J. Am. Chem. Soc., 2003,125,5139-5151.