手性磷酸催化不对称硫杂Mannich反应研究
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摘要
本论文包括以下三部分：
(1)对近年来手性磷酸催化的各种类型的不对称反应研究进展进行了综述。
(2)首次成功发展了手性磷酸不对称催化硫酚与亚胺的硫Aza-Mannich反应,通过对手性磷酸催化剂和各种实验条件的优化,成功实现了硫酚对N-酰基亚胺的不对称加成；巧妙地利用氧杂半缩醛代替N-酰基亚胺,不仅大大简化了底物的合成难度,而且使反应条件更为温和,实验操作更简便,以高产率(最高98%)和高选择性(最高99%)得到了手性硫杂半缩醛衍生物。
(3)探索了有机小分子催化的以β-萘酚为代表的几种富电子芳香化合物的不对称Friedel-Crafts烷基化反应,优化了催化剂、溶剂、温度等实验条件,以较高的产率得到了Friedel-Crafts烷基化产物,但对映选择性不够理想。
This thesis is composed of three parts:
(1) Brφnsted acid catalyses are rapidly growing areas in organocatalysis. In this part, the development of the Brφnsted acid catalyzed asymmetric reactions is illustrated from its very beginning up to the present. The progress on the chiral Bronsted acid catalysis has been reviewed with a focus being placed on addition reaction, cyclization reaction, and counteranion directed catalysis.
(2) We have developed the asymmetric addition reactions of thiophenol to N-acyl imines. The addition products were obtained in high yields (up to 98%) and excellent enantioselectivities (up to 99%) under the optimized reactions conditions. The method is applicable to not only simplifys experimental condition, but also enables facile access to highly enantioenriched chiral N-acetal derivatives.
(3) We investigated asymmetric Friedel-Crafts alkylation reaction of P-naphthol. Although, the Friedel-Crafts products could be prepared in a straightforward procedure in high yields under mild reaction conditions, enantiomeric excess is poor.
(1)对近年来手性磷酸催化的各种类型的不对称反应研究进展进行了综述。
(2)首次成功发展了手性磷酸不对称催化硫酚与亚胺的硫Aza-Mannich反应,通过对手性磷酸催化剂和各种实验条件的优化,成功实现了硫酚对N-酰基亚胺的不对称加成；巧妙地利用氧杂半缩醛代替N-酰基亚胺,不仅大大简化了底物的合成难度,而且使反应条件更为温和,实验操作更简便,以高产率(最高98%)和高选择性(最高99%)得到了手性硫杂半缩醛衍生物。
(3)探索了有机小分子催化的以β-萘酚为代表的几种富电子芳香化合物的不对称Friedel-Crafts烷基化反应,优化了催化剂、溶剂、温度等实验条件,以较高的产率得到了Friedel-Crafts烷基化产物,但对映选择性不够理想。
This thesis is composed of three parts:
(1) Brφnsted acid catalyses are rapidly growing areas in organocatalysis. In this part, the development of the Brφnsted acid catalyzed asymmetric reactions is illustrated from its very beginning up to the present. The progress on the chiral Bronsted acid catalysis has been reviewed with a focus being placed on addition reaction, cyclization reaction, and counteranion directed catalysis.
(2) We have developed the asymmetric addition reactions of thiophenol to N-acyl imines. The addition products were obtained in high yields (up to 98%) and excellent enantioselectivities (up to 99%) under the optimized reactions conditions. The method is applicable to not only simplifys experimental condition, but also enables facile access to highly enantioenriched chiral N-acetal derivatives.
(3) We investigated asymmetric Friedel-Crafts alkylation reaction of P-naphthol. Although, the Friedel-Crafts products could be prepared in a straightforward procedure in high yields under mild reaction conditions, enantiomeric excess is poor.
引文
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6. For the achiral sulfa-Michael reaction, see:a) Ramirez-Osuna, M.; Chavez, D.; Hernandez, L.; Molins, E.; Somanathan, R.; Aguirre, G. Synthesis of Analogs of Amathamide A and Their Preliminary Antimicrobial Activity. Molecules 2005,10, 295-301; b) Mickael, M.; Vincent, D. TMAF-Catalyzed Conjugate Addition of Oxazolidinone and Thiols. Synlett 2005,95-98; c) Krishnaveni, N. Srilakshmi.; Surendra, K.; Rao, K. Rama. Study of the Michael Addition of Cyclodextrin-thiol Complexes to Conjugated Alkenes in Water. Chem. Commun.2005,5,669-671; d) Rai, V.; Namboothiri, I. N. N. A Theoretical Evaluation of the Michael-Acceptor Ability of Conjugated Nitroalkenes. Eur. J. Org. Chem.2006,4693-4703; e) Chen, W. Y.; Shi, L. Ammonium Chloride-catalyzed Carbon-sulfur Bond Formation in Water. Catal. Commun.2008,1079-1081; f) Halimehjani, A. Z.; Saidi, M. R. Synthesis of aza-Henry Products and Enamines in Water by Michael Addition of Amines or Thiols to Activated Unsaturated Compounds. Tetrahedron Lett.2008,49, 1244-1248; g) Hussain, S.; Saitanya; Bharadwaj, K.; Mihir; Chaudhuri, K.; Kalita, H. Borax as an Efficient Metal-Free Catalyst for Hetero-Michael Reactions in an Aqueous Medium. Eur. J. Org. Chem.2007,374-378; h) Chu, C.M.; Tu, J. Z.; Wu, P.; Wang, C. C.; Liu, J. T.; Kuo, C. W.; Shin, Y. H.; Yao, C. F. Straightforward and Highly Efficient Catalyst-free Regioselective Reaction of Thiol to P-Nitrostyrene:a Concise Synthesis of Vinyl Sulfide and Nitro Sulfide. Tetrahedron 2009,65, 3878-3885; i) Zhdanko, Alexander. G.; Gulevich, A. V.; Nenajdenko, V. G. One-step Synthesis of.N-Acetylcysteine and Glutathione Derivatives Using the Ugi Reaction. Tetrahedron,2009,65,4692-1702.
7. For a review on asymmetric Michael additions of thiols, see:Enders, D.; Luttgen, K.; Narine, A. A. Asymmetric Sulfa-Michael Additions. Synthesis 2007,959-980. For enantioselective Michael additions of sulfur nucleophiles to α,β-unsaturated carbonyl compounds, see:a) Liu, Y.; Sun, B.; Wang, B.; Wakem, M.; Deng, L. Catalytic Asymmetric Conjugate Addition of Simple Alkyl Thiols to α,β-Unsaturated N-Acylated Oxazolidin-2-ones with Bifunctional Catalysts. J. Am. Chem. Soc.2009,131,418-419; b) Enders, D.; Hoffman, K. Organocatalytic Asymmetric Sulfa-Michael Additions to α,β-Unsaturated Sulfonates Eur. J. Org. Chem.2009,1665-1668; c) Ricci, P.; Carlone, A.; Bartoli, G.; Bosco, M.; Sambri, M.; Melchiorre, P. Organocatalytic Asymmetric Sulfa-Michael Addition to α,β-Unsaturated Ketones. Adv. Synth. Catal.2008,350,49-53; d) Abe, A. M. M.; Sauerland, S. J. K.; Koskinen, A. M. P. Highly Enantioselective Conjugate Addition of Thiols Using Mild Scandium Triflate Catalysis. J. Org. Chem.2007,72, 5411-5413; e) Ueda, E.; Miyabe, E.; Shimizu, H.; Sugino, H.; Miyata, O.; Naito, A. Regioselective Hydroxysulfenylation of α,β-Unsaturated Imines:Enhanced Stability of an Intermediate Radical. Angew. Chem. Int. Ed.2008,47,5600-5604; f) Marigo, M.; Schulte, T.; Franzen, J.; Jφrgensen, K. A. Asymmetric Multicomponent Domino Reactions and Highly Enantioselective Conjugated Addition of Thiols to α,β-Unsaturated Aldehydes J. Am. Chem. Soc.2005,127,15710-15711; g) Wang, W.; Li, H.; Wang, J.; Zu, L. Enantioselective Organocatalytic Tandem Michael-Aldol Reactions:One-Pot Synthesis of Chiral Thiochromenes J. Am. Chem. Soc.2006,128,10354-10355; h) Brandau. S.; Maerten. E.; Jφrgensen. K. A. Asymmetric Synthesis of Highly Functionalized Tetrahydrothiophenes by Organocatalytic Domino Reactions. J. Am. Chem. Soc.2006,128,14986-14991; i) Palomo, C.; Oiarbide, M.; Lopez, R. L.; Gonzaiez P. B.; Mez-Bengoa, E. G.; Sa, J. M.; Linden, A. Intramolecular Sulfur Transfer in N-Enoyl Oxazolidine-2-thiones Promoted by Brφnsted Acids. Practical Asymmetric Synthesis of p-Mercapto Carboxylic Acids and Mechanistic Insights. J. Am. Chem. Soc.2006,128, 15236-15247; j) Marigo, M.; Schulte, T.; Franz, J.; Jogensen, K. A. Asymmetric Multicomponent Domino Reactions and Highly Enantioselective Conjugated Addition of Thiols to α,β-Unsaturated Aldehydes.J. Am. Chem. Soc.2005,127, 15710-15711; k) McDaid, P.; Chen, Y.; Deng, L. A Highly Enantioselective and General Conjugate Addition of Thiols to Cyclic Enones with an Organic Catalyst. Angew. Chem. Int. Ed.2002,41,338-340; 1) Ricci, P.; Carlone, A.; Bartoli, G.; Bosco, M.; Sambri, L.; Melchiorre, P. Organocatalytic Asymmetric Sulfa-Michael Addition to α,β-Unsaturated Ketones. Adv. Synth. Catal.2008,350,49-53; m) Li, H.; Wang, J.; Zu, L. S.; Wang, W. Organocatalytic Asymmetric Conjugate addition of thioacetic acid to P-nitrostyrenes. Tetrahedron Lett.2006,47,2585-2589; n) Li, H.; Zu, Z.; Xie, H.; Wang, J.; Jiang, W.; Wang. W. Enantioselective Organocatalytic Double Michael Addition Reactions. Org. Lett.,2007,9,1833-1835.
8. For Michael additions of sulfur nucleophiles to nitroalkenes, see:a) Dodda, J. J.; Goldman, K.; Mandal, T.; Zhao, C. G.; Broker, G. A.; Tiekinka, E. R. T. Synthesis of 2,3,4-Trisubstituted Thiochromanes using an Organocatalytic Enantioselective TandemMichael-Henry Reaction. Adv. Synth. Catal.2008,350,537-541; b) Wang, J.; Xie, H. X.; Li, H.; Zu, L. S.; Wang, W. A Highly Stereoselective Hydrogen-Bond-Mediated Michael-Michael Cascade Process through Dynamic Kinetic Resolution. Angew. Chem. Int. Ed.2008,47,4177-4179; c) Kimmel, K. L.; Robak, M. T.; Ellman, J. A. Enantioselective Addition of Thioacetic Acid to Nitroalkenes via N-Sulfinyl Urea Organocatalysis. J. Am. Chem Soc.2009,131, 8754-8755; d) Lu, H. H.; Zhang, F. G.; Meng, M. G.; Duan, S. W.; Xiao, W. G. 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.
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10. Hui, X. P.; Yin, C.; Ma, J.; Xu, P. F. Green Procedure for the Synthesis of p-Nitro Sulfides by Michael Addition of Thiols to Nitroolefins. Synth. Commun.2009,39, 676-690.
11. Akiyama, T.; Itoh, J.; Yokota, K.; Fuchibe, K. Enantioselective Mannich-Type Re-action Catalyzed by a Chiral Brφnsted Acids. Angew. Chem. Int. Ed.2004,43, 1566-1568.
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13. Akiyama, T.; Morita, H.; Itoh, J.; Fuchibe, K. Chiral Bronsted Acid Catalyzed Enantioselective Hydrophosphonylation of Imines:Asymmetric Synthesis of a-Amino Phosphonates. Org. Lett.2005,7,2583-2585.
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21. a) Storer, R. I.; Carrera, D. E.; Ni, Y.; MacMillan, D. W. C. Enantioselective Organocatalytic Reductive Amination. J. Am. Chem. Soc.2006,128,84-86; b) Akiyama, T.; Itoh, J.; Yokota, K.; Fuchibe, K. Enantioselective Mannich-Type Reaction Catalyzed by a Chiral Brφnsted Acids. Angew. Chem. Int. Ed.2004,43, 1566-1568. c) Itoh, J.; Fuchibe, K.; Akiyama, T. Chiral Brφnsted Acid Catalyzed Enantioselective Aza-Diels-Alder Reaction of Brassard's Diene with Imines Angew. Chem, Int. Ed.2006,45,4796-4798; d) Zhu, S. S.; Cefalo, D. R.; La, D. S.; Jamieson, J. Y.; Davis, W. M.; Hoveyda, A. H.; Schrock, R. R. Chiral Mo-Binol Complexes:Activity, Synthesis, and Structure.Efficient Enantioselective Six-Membered Ring Synthesis through Catalytic Metathesis. J. Am. Chem. Soc. 1999,121,8251-8259. e) Akiyama, T.; Morita, H.; Itoh, J.; Fuchibe, K. Chiral Brφnsted Acid Catalyzed Enantioselective Hydrophosphonylation of Imines: Asymmetric Synthesis of α-Amino Phosphonates. Org. Lett.2005,7,2583-2585.
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8. For representative examples of chiral Lewis acids catalyzed F-C alkylations, see:a) Adachi, S.; Tanaka, F.; Watanabe, K.; Harada, T. Oxazaborolidinone-Catalyzed Enantioselective Friedel-Crafts Alkylation of Furans and Indoles with α,β-Unsaturated Ketones. Org. Lett.2009,11,5206-5209; b) Smith, A. J.; Abbott, L. K.; Martin, S. F. Enantioselective Conjugate Addition Employing 2-Heteroaryl Titanates and Zinc Reagents. Org. Lett.2009,11,4200-4203; c) Liu, Y. L.; Shang, D. J.; Zhou, X.; Liu, X. L.; Feng, X. M. Enantioselective Friedel-Crafts Alkylation of Indoles with Alkylidene Malonates Catalyzed by N,N'-Dioxide-Scandium(Ⅲ) Complexes:Asymmetric Synthesis of β-Carbolines. Chem. Eur. J.2009,15,2055-2058; d) Stecher, H.; Tengg, M.; Ueberbacher, B. J.; Remler, P.; Schwab, H.; Griengl, H.; Khadjawi, M. G. Biocatalytic Friedel-Crafts Alkylation Using Non-natural Cofactors. Angew. Chem. Int. Ed.2009,48,9546-9548; e) Boersma, A.J.; Feringa, B. L.; Roelfes, G. Enantioselective Friedel-Crafts Reactions in Water Using a DNA Based Catalyst. Angew. Chem. Int. Ed.2009,48,3346-3348; f) Sibi, M. P.; Coulomb, J.; Stanley, L. M. Enantioselective Enolate Protonations: Friedel-Crafts Reactions with α-Substituted Acrylates. Angew. Chem. Int. Ed.2008, 47,9913-9915; g) Schaetz, A.; Rasappan, R.; Hager, M.; Gissibl, A.; Reiser, O. Dependence of Enantioselectivity on the Ligand/Metal Ratio in the Asymmetric Michael Addition of Indole to Benzylidene Malonates:Electronic Influence of Substrates. Chem. Eur. J.2008,14,7259-7265; h) Evans, D. A.; Fandrick, K. R. Song, H. J.; Scheidt, K. A.; Xu, R. S. Enantioselective Friedel-Crafts Alkylations Catalyzed by Bis(oxazolinyl)-pyridine-Scandium(Ⅲ) Triflate Complexes. J. Am. Chem. Soc.2007,129,10029-10041; i) Evans, D. A.; Fandrick, K. R.; Song, H. J. Enantioselective Friedel-Crafts Alkylations of a, (3-Unsaturated 2-Acyl Imidazoles Catalyzed by Bis(oxazolinyl)-pyridine-Scandium(Ⅲ) Triflate Complexes.J. Am. Chem. Soc.2005,127,8942-8943; j) Takenaka, N.; Abell, J. P.; Yamamoto, H. Asymmetric Conjugate Addition of Silyl Enol Ethers Catalyzed by Tethered Bis(8-quinolinolato) Aluminum Complexes.J. Am. Chem. Soc.2007,129,742-743; k) Liu, H.; Lu, S. F.; Xu, J. X.; Du, D. M. Asymmetric Friedel-Crafts Alkylation of Electron-Rich N-Heterocycles with Nitroalkenes Catalyzed by Diphenylamine-Tethered Bis(oxazoline) and Bis (thiazoline)Zn(Ⅱ) Complexes. Chem. Asian J.2008, 3,1111-1121.
9. For representative examples of chiral Brφnsted acid catalyzed F-C alkylations, see: a) Jiang, H.; Paixao, M. W.; David, M.; Jφrgensen, K. A. Acyl Phosphonates:Good Hydrogen Bond Acceptors and Ester/Amide Equivalents in Asymmetric Organocatalysis. J. Am. Chem. Soc.2010,132,2775-2783; b) Sheng, Y. F.; Gu, Q.; Zhang, A. J.; You, S. L. Chiral Brφnsted Acid-Catalyzed Asymmetric Friedel-Crafts Alkylation of Pyrroles with Nitroolefins. J. Org. Chem.2009,74,6899-6901; c) Zeng, M.; Kang, Q.; He, Q. L.; You, S. L. Highly Enantioselective Friedel-Crafts Reaction of 4,7-Dihydroindoles with β,γ-Unsaturated α-Keto Esters by Chiral Brφnsted Acids. Adv. Synth. Catal.2008,350,2169-2173; d) Rueping, M.; Nachtsheim, B. J.; Moreth, S. A.; Bolte, M. Asymmetric Brφnsted Acid Catalysis: Enantioselective Nucleophilic Substitutions and 1,4-Additions. Angew. Chem. Int. Ed.2008,47,593-596; e) Itoh, J. J.; Fuchibe, K. H.; Akiyama, K. Chiral Phosphoric Acid Catalyzed Enantioselective Friedel-Crafts Alkylation of Indoles with Nitro-alkenes.:Cooperative Effect of 3A Molecular Sieves. Angew. Chem. Int. Ed.2008, 47,4016-4018; f) Herrera, R. P.; Sgarzani, V.; Bernardi, L.; Ricci, A. Catalytic Enantioselective Friedel-Crafts Alkylation of Indoles with Nitroalkenes by Using a Simple Thiourea Organocatalyst. Angew. Chem. Int. Ed.2005,44,6576-6579; g) Ganesh, M.; Seidel, D. Catalytic Enantioselective Additions of Indoles to Nitroalkenes. J. Am. Chem. Soc.2008,130,16464-16465; h) Sheng, Y. F.; Li, G. Q.; Kang, Q.; Zhang, A. J.; You, S. L. Asymmetric Friedel-Crafts Reaction of 4,7-Dihydroindoles with Nitroolefins by Chiral Brφnsted Acids under Low Catalyst Loading. Chem. Eur. J.2009,15,3351-3354.
10. For representative examples of chiral primary or secondary amine catalyzed F-C alkylations, see:a) Hong, L.; Liu, C. X.; Sun, W. S.; Wang, L.; Wong, K. K.; Wang, R. Organocatalytic Enantioselective Friedel-Crafts Alkylation of 4,7-Dihydroindoles with α,β-Unsaturated Aldehydes:An Easy Access to 2-Substituted Indoles. Org. Lett.2009,11,2177-2180; b) Galzerano, P.; Pesciaioli, F.; Mazzanti, A.; Bartoli, G.; Melchiorre, P. Asymmetric Organocatalytic Cascade Reactions with a-Substituted α,β-Unsaturated Aldehydes. Angew. Chem. Int. Ed. 2009,48,7892-7894; c) Chi, Y. G.; Scroggins, S. T.; Frechet, J. M. J. One-Pot Multi-Component Asymmetric Cascade Reactions Catalyzed by Soluble Star Polymers with Highly Branched Non-Interpenetrating Catalytic Cores.J. Am. Chem. Soc.2008,130,6322-6323; d) Li, C. F.; Liu, H.; Liao, J.; Cao, Y. J.; Liu, X. P.; Xiao, W. J. Enantioselective Organocatalytic Intramolecular Ring-Closing Friedel-Crafts-Type Alkylation of Indoles. Org. Lett.2007,9,1847-1850; e) Bartoli, G.; Bosco, M.; Carlone, A.; Pesciaioli, F.; Sambri, L.; Melchiorre, P. Organocatalytic Asymmetric Friedel-Crafts Alkylation of Indoles with Simple α,β-Unsaturated Ketones. Org. Lett.2007,7,1403-1405; f) King, H. D.; Meng, Z. X.; Denhart, D.; Mattson, R.; Kimura, R.; Wu, D. D.; Gao, Q.; Macor, J. E. Enantioselective Synthesis of a Highly Potent Selective Serotonin Reuptake Inhibitor. An Application of Imidazolidinone Catalysis to the Alkylation of Indoles with an α,β-Disubstituted α,β-Unsaturated Aldehyde. Org. Lett.2005,7, 3437-3440; g) Huang, Y.; Walji, B. M.; Larsen, C. H.; MacMillan, D. W. C. Enantioselective Organo-Cascade Catalysis. J. Am. Chem. Soc.2005,127, 15051-15053; h) Austin, J. F.; MacMillan, D. W. C. Enantioselective Organo-catalytic Indole Alkylations. Design of a New and Highly Effective Chiral Amine for Iminium Catalysis. J. Am. Chem. Soc.2002,124,1172-1173.
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8. For representative examples of chiral Lewis acids catalyzed F-C alkylations, see:a) Adachi, S.; Tanaka, F.; Watanabe, K.; Harada, T. Oxazaborolidinone-Catalyzed Enantioselective Friedel-Crafts Alkylation of Furans and Indoles with α,β-Unsaturated Ketones. Org. Lett.2009,11,5206-5209; b) Smith, A. J.; Abbott, L. K.; Martin, S. F. Enantioselective Conjugate Addition Employing 2-Heteroaryl Titanates and Zinc Reagents. Org. Lett.2009,11,4200-4203; c) Liu, Y. L.; Shang, D. J.; Zhou, X.; Liu, X. L.; Feng, X. M. Enantioselective Friedel-Crafts Alkylation of Indoles with Alkylidene Malonates Catalyzed by N,N'-Dioxide-Scandium(Ⅲ) Complexes:Asymmetric Synthesis of β-Carbolines. Chem. Eur. J.2009,15,2055-2058; d) Stecher, H.; Tengg, M.; Ueberbacher, B. J.; Remler, P.; Schwab, H.; Griengl, H.; Khadjawi, M. G. Biocatalytic Friedel-Crafts Alkylation Using Non-natural Cofactors. Angew. Chem. Int. Ed.2009,48,9546-9548; e) Boersma, A.J.; Feringa, B. L.; Roelfes, G. Enantioselective Friedel-Crafts Reactions in Water Using a DNA Based Catalyst. Angew. Chem. Int. Ed.2009,48,3346-3348; f) Sibi, M. P.; Coulomb, J.; Stanley, L. M. Enantioselective Enolate Protonations: Friedel-Crafts Reactions with α-Substituted Acrylates. Angew. Chem. Int. Ed.2008, 47,9913-9915; g) Schaetz, A.; Rasappan, R.; Hager, M.; Gissibl, A.; Reiser, O. Dependence of Enantioselectivity on the Ligand/Metal Ratio in the Asymmetric Michael Addition of Indole to Benzylidene Malonates:Electronic Influence of Substrates. Chem. Eur. J.2008,14,7259-7265; h) Evans, D. A.; Fandrick, K. R. Song, H. J.; Scheidt, K. A.; Xu, R. S. Enantioselective Friedel-Crafts Alkylations Catalyzed by Bis(oxazolinyl)-pyridine-Scandium(Ⅲ) Triflate Complexes. J. Am. Chem. Soc.2007,129,10029-10041; i) Evans, D. A.; Fandrick, K. R.; Song, H. J. Enantioselective Friedel-Crafts Alkylations of a, (3-Unsaturated 2-Acyl Imidazoles Catalyzed by Bis(oxazolinyl)-pyridine-Scandium(Ⅲ) Triflate Complexes.J. Am. Chem. Soc.2005,127,8942-8943; j) Takenaka, N.; Abell, J. P.; Yamamoto, H. Asymmetric Conjugate Addition of Silyl Enol Ethers Catalyzed by Tethered Bis(8-quinolinolato) Aluminum Complexes.J. Am. Chem. Soc.2007,129,742-743; k) Liu, H.; Lu, S. F.; Xu, J. X.; Du, D. M. Asymmetric Friedel-Crafts Alkylation of Electron-Rich N-Heterocycles with Nitroalkenes Catalyzed by Diphenylamine-Tethered Bis(oxazoline) and Bis (thiazoline)Zn(Ⅱ) Complexes. Chem. Asian J.2008, 3,1111-1121.
9. For representative examples of chiral Brφnsted acid catalyzed F-C alkylations, see: a) Jiang, H.; Paixao, M. W.; David, M.; Jφrgensen, K. A. Acyl Phosphonates:Good Hydrogen Bond Acceptors and Ester/Amide Equivalents in Asymmetric Organocatalysis. J. Am. Chem. Soc.2010,132,2775-2783; b) Sheng, Y. F.; Gu, Q.; Zhang, A. J.; You, S. L. Chiral Brφnsted Acid-Catalyzed Asymmetric Friedel-Crafts Alkylation of Pyrroles with Nitroolefins. J. Org. Chem.2009,74,6899-6901; c) Zeng, M.; Kang, Q.; He, Q. L.; You, S. L. Highly Enantioselective Friedel-Crafts Reaction of 4,7-Dihydroindoles with β,γ-Unsaturated α-Keto Esters by Chiral Brφnsted Acids. Adv. Synth. Catal.2008,350,2169-2173; d) Rueping, M.; Nachtsheim, B. J.; Moreth, S. A.; Bolte, M. Asymmetric Brφnsted Acid Catalysis: Enantioselective Nucleophilic Substitutions and 1,4-Additions. Angew. Chem. Int. Ed.2008,47,593-596; e) Itoh, J. J.; Fuchibe, K. H.; Akiyama, K. Chiral Phosphoric Acid Catalyzed Enantioselective Friedel-Crafts Alkylation of Indoles with Nitro-alkenes.:Cooperative Effect of 3A Molecular Sieves. Angew. Chem. Int. Ed.2008, 47,4016-4018; f) Herrera, R. P.; Sgarzani, V.; Bernardi, L.; Ricci, A. Catalytic Enantioselective Friedel-Crafts Alkylation of Indoles with Nitroalkenes by Using a Simple Thiourea Organocatalyst. Angew. Chem. Int. Ed.2005,44,6576-6579; g) Ganesh, M.; Seidel, D. Catalytic Enantioselective Additions of Indoles to Nitroalkenes. J. Am. Chem. Soc.2008,130,16464-16465; h) Sheng, Y. F.; Li, G. Q.; Kang, Q.; Zhang, A. J.; You, S. L. Asymmetric Friedel-Crafts Reaction of 4,7-Dihydroindoles with Nitroolefins by Chiral Brφnsted Acids under Low Catalyst Loading. Chem. Eur. J.2009,15,3351-3354.
10. For representative examples of chiral primary or secondary amine catalyzed F-C alkylations, see:a) Hong, L.; Liu, C. X.; Sun, W. S.; Wang, L.; Wong, K. K.; Wang, R. Organocatalytic Enantioselective Friedel-Crafts Alkylation of 4,7-Dihydroindoles with α,β-Unsaturated Aldehydes:An Easy Access to 2-Substituted Indoles. Org. Lett.2009,11,2177-2180; b) Galzerano, P.; Pesciaioli, F.; Mazzanti, A.; Bartoli, G.; Melchiorre, P. Asymmetric Organocatalytic Cascade Reactions with a-Substituted α,β-Unsaturated Aldehydes. Angew. Chem. Int. Ed. 2009,48,7892-7894; c) Chi, Y. G.; Scroggins, S. T.; Frechet, J. M. J. One-Pot Multi-Component Asymmetric Cascade Reactions Catalyzed by Soluble Star Polymers with Highly Branched Non-Interpenetrating Catalytic Cores.J. Am. Chem. Soc.2008,130,6322-6323; d) Li, C. F.; Liu, H.; Liao, J.; Cao, Y. J.; Liu, X. P.; Xiao, W. J. Enantioselective Organocatalytic Intramolecular Ring-Closing Friedel-Crafts-Type Alkylation of Indoles. Org. Lett.2007,9,1847-1850; e) Bartoli, G.; Bosco, M.; Carlone, A.; Pesciaioli, F.; Sambri, L.; Melchiorre, P. Organocatalytic Asymmetric Friedel-Crafts Alkylation of Indoles with Simple α,β-Unsaturated Ketones. Org. Lett.2007,7,1403-1405; f) King, H. D.; Meng, Z. X.; Denhart, D.; Mattson, R.; Kimura, R.; Wu, D. D.; Gao, Q.; Macor, J. E. Enantioselective Synthesis of a Highly Potent Selective Serotonin Reuptake Inhibitor. An Application of Imidazolidinone Catalysis to the Alkylation of Indoles with an α,β-Disubstituted α,β-Unsaturated Aldehyde. Org. Lett.2005,7, 3437-3440; g) Huang, Y.; Walji, B. M.; Larsen, C. H.; MacMillan, D. W. C. Enantioselective Organo-Cascade Catalysis. J. Am. Chem. Soc.2005,127, 15051-15053; h) Austin, J. F.; MacMillan, D. W. C. Enantioselective Organo-catalytic Indole Alkylations. Design of a New and Highly Effective Chiral Amine for Iminium Catalysis. J. Am. Chem. Soc.2002,124,1172-1173.
11. Niu, L. F.; Xin, Y. C.; Wang, R. L.; Jiang, F.; Xu, P. F.; Hui, X. P. Asymmetric Aza-Friedel-Crafts Reaction of 2-Naphthol with Tosylimines Catalyzed by a Dinuclear Zinc Complex. Synlett 2010,765-768.
12. a) Storer, R. I.; Carrera, D. E.; Ni, Y.; MacMillan, D. W. C. Enantioselective Organocatalytic Reductive Amination. J. Am. Chem. Soc.2006,128,84-86; b) Akiyama, T.; Itoh, J.; Yokota, K.; Fuchibe, K. Enantioselective Mannich-Type Reaction Catalyzed by a Chiral Brφnsted Acids. Angew. Chem. Int. Ed.2004,43, 1566-1568. c) Itoh, J.; Fuchibe, K.; Akiyama, T. Chiral Brφnsted Acid Catalyzed Enantioselective Aza-Diels-Alder Reaction of Brassard's Diene with Imines. Angew. Chem. Int. Ed.2006,45,4796-4798; d) Zhu, S. S.; Cefalo, D. R.; La, D. S.; Jamieson, J. Y.; Davis, W. M.; Hoveyda, A. H.; Schrock, R. R. Chiral Mo-Binol Complexes:Activity, Synthesis, and Structure.Efficient Enantioselective Six-Membered Ring Synthesis through Catalytic Metathesis. J. Am. Chem. Soc. 1999,121,8251-8259; e) Akiyama, T.; Morita, H.; Itoh, J.; Fuchibe, K. Chiral Brφnsted Acid Catalyzed Enantioselective Hydrophosphonylation of Imines: Asymmetric Synthesis of α-Amino Phosphonates. Org. Lett.2005,7,2583-2585; d) Singh, R.; Czekelius, C.; Schrock, R. R.; Mller, P.; Hoveyda, A. H. Molybdenum Imido Alkylidene Metathesis Catalysts That Contain Electron-Withdrawing Biphenolates or Binaphtholates. Organometallics.2007,26,2528-2539.
13. Nakashima, D.; Yamamoto, H. Design of Chiral N-Triflyl Phosphoramide as a Strong Chiral Bronsted Acid and Its Application to Asymmetric Diels-Alder Reaction. J. Am. Chem. Soc.2006,128,9626-9627.
14. a) Uraguchi, D.; Sorimachi, K.; Terada, M. Organocatalytic Asymmetric Direct Alkylation of a-Diazoester via C-H Bond Cleavage. J. Am. Chem. Soc.2005,127, 9360-9361; b) Terada, M.; Machioka, K.; Sorimachi, K. High Substrate/Catalyst Organocatalysis by a Chiral Bransted Acid for an Enantioselective Aza-Ene-Type Reaction. Angew. Chem. Int. Ed.2006,45,2254-2259; c) Katritzky, A. R.; Pernak, J.; Fan, W.; Saczewski, F.N-(1-Benzotriazol-1-ylalkyl)amides, Versatile alpha-amidoalkylation reagents alpha-Amidoalkylation of CH acids. J. Org. Chem.1991, 56,4439-4443; d) Katritzky, A. R.; Fan, W. Black, M.; Pernak, J. N-[1-(Benzo-triazol-1-yl)alkyl]amides, versatile amidoalkylation reagents. A General and Con-venient Route to N-(alpha-alkoxyalkyl)amides. J. Org. Chem.1992,57,547-549; e) Jennings, W. B.; Lovely, C. J. The Titanium Tetrachloride Induced Synthesis of N-Phosphinoylimines and N-Sulphonylimines Directly from Aromatic Aldehydes. Tetrahedron,1991,47,5561-5568.