不对称催化合成手性五元和三元杂环
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摘要
很多天然产物、具有生物活性和药物活性的分子、多功能材料以及重要的有机合成中间体中都含有手性杂环结构单元。不对称催化合成手性杂环化合物是非常直接有效的方法,因此受到了很多有机化学家的关注。本文分别介绍了不对称催化合成手性的咪唑烷和顺式缩水甘油酰胺的新方法。
光学活性的咪唑烷是一类有着广泛用途的有机合成中间体。亚胺叶立德和亚胺的1,3-偶极环加成反应,一步构建多个手性中心,是合成咪唑烷非常有效和原子经济的方法。到目前为止,不对称催化的亚胺叶立德和亚胺之间的1,3-偶极环加成反应还没有报道,这也说明不对称催化合成手性咪唑烷是一个难题。本文首次报道了手性布朗斯特酸催化的亚胺叶立德和亚胺之间的1,3-偶极环加成反应。醛、胺基酯和芳香胺—锅反应,高立体选择性地得到手性的咪唑烷。反应呈现负的非线性效应,由此我们推测反应的机理是两分子磷酸分别活化亚胺叶立德和亚胺的双活化过程。同时,该反应进一步说明手性布朗斯特酸活化的1,3-偶极子是一类重要的不对称1,3-偶极环加成反应的中间体。
光学活性的缩水甘油酯和酰胺是一类非常重要的手性分子。合成该类分子的方法已经报道很多,并且取得了很大的成功,主要包括α,β-不饱和化合物的不对称环氧化和Darzens反应。但是关于顺式缩水甘油酯和酰胺的立体专一性合成的报道不多。本文报道了一例高立体选择性和高对映选择性的Darzens反应,即通过四异丙氧钛和(R)-联二萘酚原位制备手性钛配合物作为催化剂,催化醛和重氮乙酰胺反应,合成高光学活性的缩水甘油酰胺。该方法底物范围非常广,芳香醛、杂芳香醛、不饱和醛以及脂肪醛都能很好的参与反应,并取得非常好的结果。我们利用该反应成功实现了抗癌药物Taxol侧链和药物中间体(-)-Bestatin的合成。
Chiral heterocyclic molecules are core structural element present in numerous natural products, biological active molecules and mutifuctional material, as well as important building blocks in organic synthesis. Catalytic asymmetric methods to access these compounds would be hihyly valuable and had attracted organic chemists' great interest. In this manuscript, we have developed two new approaches for catalytical asymmetric synthesis of optically active imidazolidines and cis-glycidic amides, respectively.
Optically active imidazolidines are important intermediates with broad applications to organic synthesis. The 1,3-dipolar cycloaddition of azomethine ylides to imines with concomitant creation of multiple stereogenic centers represents an efficient and atom-economic method for the manufacture of these compounds. However, to date, the catalytic asymmetric 1,3-dipolar cycloaddition of azomethine ylides to imines has not yet appeared and therefore remains an important challenge. In this manuscript, we have described the first Br(?)nsted acid catalyzed asymmetric 1, 3-dipolar cycloaddition between azomethine ylides and imines that directly assembles aldehydes, amino esters, and anilines into synthetically useful chiral imidazolidines with high levels of stereoselectivity. The negative NLE revealed two molecules of chiral phosphoric acids participated in the catalysis by the activation of both azomethine ylides and imines. This reaction has further demonstrated that the chiral Br(?)nsted acid-activated dipoles are versatile intermediates for the creation of new enantioselective 1,3-dipolar cycloadditions.
The optically active glycidic esters and amides have.been one of the most of important classes of chiral molecules. The well established methods to access these optical compounds include asymmetric catalytic epoxidation ofα,β-unsaturated carbonyl compounds and Darzens reaction. Despite these elegant advances, relatively few protocols have been available for accessing either the cis-glycidic esters or amides. We have described a highly diastereo-and enantioselective Darzens reaction of aldehydes with diazoacetamides catalyzed by a chiral titanium complex formed in situ from commercially available Ti(O-i-Pr)4 and (R)-binaphthol, solely giving cis-glycidic amides with excellent enantiomeric purity. The protocol tolerated a broad scope of structurally diverse aldehydes, including aromatic, heteroatomatic, unsaturated, and aliphatic aldehydes. This new method has high potential in the enantioselective synthesis of biologically active substances as demonstrated by the preparation of the side chains of taxol and the chiral building block of (-)-bestatin.
光学活性的咪唑烷是一类有着广泛用途的有机合成中间体。亚胺叶立德和亚胺的1,3-偶极环加成反应,一步构建多个手性中心,是合成咪唑烷非常有效和原子经济的方法。到目前为止,不对称催化的亚胺叶立德和亚胺之间的1,3-偶极环加成反应还没有报道,这也说明不对称催化合成手性咪唑烷是一个难题。本文首次报道了手性布朗斯特酸催化的亚胺叶立德和亚胺之间的1,3-偶极环加成反应。醛、胺基酯和芳香胺—锅反应,高立体选择性地得到手性的咪唑烷。反应呈现负的非线性效应,由此我们推测反应的机理是两分子磷酸分别活化亚胺叶立德和亚胺的双活化过程。同时,该反应进一步说明手性布朗斯特酸活化的1,3-偶极子是一类重要的不对称1,3-偶极环加成反应的中间体。
光学活性的缩水甘油酯和酰胺是一类非常重要的手性分子。合成该类分子的方法已经报道很多,并且取得了很大的成功,主要包括α,β-不饱和化合物的不对称环氧化和Darzens反应。但是关于顺式缩水甘油酯和酰胺的立体专一性合成的报道不多。本文报道了一例高立体选择性和高对映选择性的Darzens反应,即通过四异丙氧钛和(R)-联二萘酚原位制备手性钛配合物作为催化剂,催化醛和重氮乙酰胺反应,合成高光学活性的缩水甘油酰胺。该方法底物范围非常广,芳香醛、杂芳香醛、不饱和醛以及脂肪醛都能很好的参与反应,并取得非常好的结果。我们利用该反应成功实现了抗癌药物Taxol侧链和药物中间体(-)-Bestatin的合成。
Chiral heterocyclic molecules are core structural element present in numerous natural products, biological active molecules and mutifuctional material, as well as important building blocks in organic synthesis. Catalytic asymmetric methods to access these compounds would be hihyly valuable and had attracted organic chemists' great interest. In this manuscript, we have developed two new approaches for catalytical asymmetric synthesis of optically active imidazolidines and cis-glycidic amides, respectively.
Optically active imidazolidines are important intermediates with broad applications to organic synthesis. The 1,3-dipolar cycloaddition of azomethine ylides to imines with concomitant creation of multiple stereogenic centers represents an efficient and atom-economic method for the manufacture of these compounds. However, to date, the catalytic asymmetric 1,3-dipolar cycloaddition of azomethine ylides to imines has not yet appeared and therefore remains an important challenge. In this manuscript, we have described the first Br(?)nsted acid catalyzed asymmetric 1, 3-dipolar cycloaddition between azomethine ylides and imines that directly assembles aldehydes, amino esters, and anilines into synthetically useful chiral imidazolidines with high levels of stereoselectivity. The negative NLE revealed two molecules of chiral phosphoric acids participated in the catalysis by the activation of both azomethine ylides and imines. This reaction has further demonstrated that the chiral Br(?)nsted acid-activated dipoles are versatile intermediates for the creation of new enantioselective 1,3-dipolar cycloadditions.
The optically active glycidic esters and amides have.been one of the most of important classes of chiral molecules. The well established methods to access these optical compounds include asymmetric catalytic epoxidation ofα,β-unsaturated carbonyl compounds and Darzens reaction. Despite these elegant advances, relatively few protocols have been available for accessing either the cis-glycidic esters or amides. We have described a highly diastereo-and enantioselective Darzens reaction of aldehydes with diazoacetamides catalyzed by a chiral titanium complex formed in situ from commercially available Ti(O-i-Pr)4 and (R)-binaphthol, solely giving cis-glycidic amides with excellent enantiomeric purity. The protocol tolerated a broad scope of structurally diverse aldehydes, including aromatic, heteroatomatic, unsaturated, and aliphatic aldehydes. This new method has high potential in the enantioselective synthesis of biologically active substances as demonstrated by the preparation of the side chains of taxol and the chiral building block of (-)-bestatin.
引文
[1]柏再苏,五大翔.2004.杂环化学：化学工业出版社.
[2]尤启东,林国强.2003.手性药物-研究与应用：化学工业出版社.
[3]Bredig G, Fiske WS, Biochem Z 1912,7
[4]List B, Lerner R A, Barbas III CF. Proline-Catalyzed Direct Asymmetric Aldol Reactions[J]. J. Am. Chem. Soc.,2000,122:2395-2396.
[5]Ahrendt K A, Borths C J, MacMillan DWC. New Strategies for Organic Catalysis:The First Highly Enantioselective Organocatalytic Diels-Alder Reaction[J]. J. Am. Chem. So.,2000,122: 4243-4244.
[6]Mukherjee S, Yang JW, Hoffmann S, List B. Asymmetric Enamine Catalysis[J]. Chem. Rev., 2007,107:5471-5569.
[7]Erkkila A, Majander I, Pihko PM. Iminium Catalysis[J]. Chem. Rev.,2007,107:5416-5470.
[8]Doyle A G, Jacobsen E N. Small-Molecule H-Bond Donors in Asymmetric Catalysis[J]. Chem. Rev.,2007,107:5713-5743.
[9]a) Akiyama T. Stronger Br(?)nsted acids[J]. Chem. Rev.,2007,107:5744-5758. b) Terada M. Binaphthol-derived phosphoric acid as a versatile catalyst for enantioselective carbon-carbon bond forming reactions[J]. Chem. Commun.2008,4097-4112.
[10]Hashimoto T, Maruoka KJ. Recent Development and Application of Chiral Phase-Transfer Catalysts[J]. Chem. Rev.,2007,107:5656-5682.
[11]Enders D, Niemeier O, Henseler A. Organocatalysis by N-Heterocyclic Carbenes[J]. Chem. Rev.,2007,107:5606-5655.
[12]a) Kobayashi S, Ishitani H. Catalytic Enantioselective Addition to Imines[J]. Chem. Rev., 1999,99:1069-1094. b) Johnson JS, Evans DA. Chiral Bis(oxazoline) Copper(Ⅱ) Complexes: Versatile Catalysts for Enantioselective Cycloaddition, Aldol, Michael, and Carbonyl Ene Reactions[J]. Acc. Chem. Res.,2000,33:325-335.
[13]a) Sigman MS, Jacobsen EN. Schiff Base Catalysts for the Asymmetric Strecker Reaction Identified and Optimized from Parallel Synthetic Libraries[J]. J. Am. Chem. Soc.1998,120: 4901-4902. b) Huang Y, Unni AK, Thadani AN, Rawal VH. Hydrogen Bonding:Single Enantiomers from a Chiral-alcohol Catalyst[J]. Nature 2003,424:146-146.
[14]a) Akiyama T, Itoh J, Yokota K, Fuchibe K. Enantioselective Mannich-Type Reaction Catalyzed by a Chiral Br(?)nsted Acid[J]. Angew.. Chem. Int. Ed.,2004,43:1566-1568. b) Yamanaka M, Itoh J, Fuchibe K, Akiyama T. Chiral Br(?)nsted Acid Catalyzed Enantioselective Mannich-Type Reaction[J]. J. Am. Chem. Soc.2007,129:6756-6764. c) Uraguchi D,Terada M. Chiral Br(?)nsted Acid-Catalyzed Direct Mannich Reactions via Electrophilic Activation[J]. J. Am. Chem. Soc.2004,126:5356-5357.
[15]Guo QX, Liu H, Guo C, Luo SW, Gu Y, Gong LZ. Chiral Br(?)nsted Acid-Catalyzed Direct Asymmetric Mannich Reaction[J]. J. Am. Chem. Soc.2007,129:3790-379.
[16]a) Sickert M, Schneider C. The Enantioselective, Br(?)nsted Acid-Catalyzed, Vinylogous Mannich Reaction[J]. Angew. Chem. Int. Ed.2008,47:3631-3634. b) Giera DS, Sickert M, Schneider C. Br(?)nsted Acid-Catalyzed, Enantioselective, Vinylogous Mannich Reaction of Vinylketene Silyl N,O-Acetals[J]. Org. Lett.2008,10:4259-4262.
[17]Uraguchi D, Sorimachi K, Terada M. Organocatalytic Asymmetric Aza-Friedel-Crafts Alkylation of Furan[J]. J. Am. Chem. Soc.2004,126:11804-11805.
[18]a) Terada M, Sorimachi K. Enantioselective Friedel-Crafts Reaction of Electron-Rich Alkenes Catalyzed by Chiral Br(?)nsted Acid[J]. J. Am. Chem. Soc.2007,129:292-293. b) Jia YX, Zhong J, Zhu SF, Zhang CM, Zhou QL. Chiral Br(?)nsted Acid Catalyzed Enantioselective Friedel-Crafts Reaction of Indoles and a-Aryl Enamides:Construction of Quaternary Carbon Atoms[J]. Angew. Chem. Int. Ed.2007,46:5565-5567. c) Kang Q, Zhao ZA, You SL. Highly Enantioselective Friedel-Crafts Reaction of Indoles with Imines by a Chiral Phosphoric Acid[J]. J. Am. Chem. Soc.2007,129:1484-1485.
[19]a) Seayad J, Seayad AM, List B. Catalytic Asymmetric Pictet-Spengler Reaction[J]. J. Am. Chem. Soc. 2006,128:1086-1087. b) Wanner M J, Haas R, Cuba.K, Maarseveen J, Hiemstra H. Catalytic Asymmetric Pictet-Spengler Reactions via Sulfenyliminium Ions[J]. Angew. Chem. Int. Ed.2007,46:7485-7487.
[20]Muratore ME, Holloway C A, Pilling A, Storer RI, Trevitt G, Dixon DJ. Enantioselective Br(?)nsted Acid-Catalyzed N-Acyliminium Cyclization Cascades[J]. J. Am. Chem. Soc.2009,131: 10796-10797.
[21]Akiyama T, Itoh J, Fuchibe K. Chiral Br(?)nsted Acid Catalyzed Enantioselective Aza-Diels-Alder Reaction of Brassard's Diene with Imines[J]. Angew. Chem. Int. Ed.2006,45: 4796-4798.
[22]a) Akiyama T, Morita H, Fuchibe K. Chiral Br(?)nsted Acid-Catalyzed Inverse Electron-Demand Aza Diels-Alder Reaction[J]. J. Am. Chem. Soc.2006,128:13070-13071. b) Liu H, Dagousset G, Masson G, Retailleau P, Zhu JP. Chiral Br(?)nsted Acid-Catalyzed Enantioselective Three-Component Pavarov Reaction[J]. J. Am. Chem. Soc.2009,131: 4598-4599.
[23]a) Liu H, Cun LF, Mi AQ, Jiang YZ, Gong LZ. Enantioselective Direct Aza Hetero-Diels-Alder Reaction Catalyzed by Chiral Br(?)nsted Acids[J]. Org. Lett.2006,8: 6023-6026. b) Rueping, M.; Azap,C.; Effective Interplay of Two Br(?)nsted Acids in the Asymmetric Synthesis of Isoquinuclidines[J]. Angew. Chem. Int. Ed.2006,45:7832-7835.
[24]a) Rueping M, Sugiono E, Azap C, Theissmann T, Bolte M. Enantioselective Br(?)nsted Acid Catalyzed Transfer Hydrogenation:Organocatalytic Reduction of Imines[J]. Org.Lett.2005,7: 3781-3783. b) Hoffmann S, Seayad A M, List B. A Powerful Br(?)nsted Acid Catalyst for the Organocatalytic Asymmetric Transfer Hydrogenation of Imines[J]. Angew.Chem., Int. Ed.2005, 44:7424-7427. c) Storer RI, Carrera DE, Ni Y, MacMillan DWC. Enantioselective Organocatalytic Reductive Amination[J]. J. Am. Chem. Soc.2006,128:84-86. d) Li G, Liang Y, Antilla JC. A Vaulted Biaryl Phosphoric Acid-Catalyzed Reduction of a-Imino Esters:The Highly Enantioselective Preparation of a-Amino Esters[J]. J. Am. Chem. Soc.2007,129: 5830-5831. e) Kang Q, Zhao ZA, You SL. Highly Enantioselective Transfer Hydrogenation of a-Imino Esters by a Phosphoric Acid[J]. Adv. Synth. Catal.2007,349:1657-1660. f) Kang Q, Zhao ZA, You SL. Asymmetric Transfer Hydrogenation of β,γ-Alkynyl a-Imino Esters by a Br(?)nsted Acid[J].Org. Lett.2008,10:2031-2034.
[25]a) Rueping M, Antonchick AP, Theissmann T. A Highly Enantioselective Br(?)nsted Acid Catalyzed Cascade Reaction:Organocatalytic Transfer Hydrogenation of Quinolines and their Application in the Synthesis of Alkaloids[J]. Angew. Chem., Int. Ed.2006,45:3683-3686. b) Rueping M, Antonchick AP, Theissmann T. Remarkably Low Catalyst Loading in Br(?)nsted Acid Catalyzed Transfer Hydrogenations:Enantioselective Reduction of Benzoxazines, Benzothiazines, and Benzoxazinones[J]. Angew. Chem., Int. Ed.2006,45:6751-6755.
[26]a) Mayer S, List B. Asymmetric Counteranion-Directed Catalysis[J]. Angew. Chem. Int. Ed. 2006,45:4193-4195. b) Yang JW, Hechavarria Fonseca MT, Vignola N, List B. Metal-Free, Organocatalytic Asymmetric Transfer Hydrogenation of a,β-unsaturated Aldehydes[J]. Angew. Chem. Int. Ed.2005,44:108-110. c) Ouellet S. G, Tuttle JB, MacMillan DWC. Enantioselective Organocatalytic Hydride Reduction[J]. J. Am. Chem. Soc.2005,127:32-33. d) Martin NJA, List B. Highly Enantioselective Transfer Hydrogenation of α,β-Unsaturated Ketones[J]. J. Am. Chem. Soc.2006,128:13368-13369.
[27]Hoffmann S, Nicoletti M, List B. Catalytic Asymmetric Reductive Amination of Aldehydes via Dynamic Kinetic Resolution[J]. J. Am. Chem. Soc.2006,128:13074-13075.
[28]a) Chen XH, Xu XY, LiuH, Cun LF, Gong LZ. Highly Enantioselective Organocatalytic Biginelli Reaction[J]. J. Am. Chem. Soc.2006,128:14802-14803. b) Li N, Chen XH, Song J, Luo SW, Fan W. Gong LZ. Highly Enantioselective Organocatalytic Biginelli and Biginelli-Like Condensations:Reversal of the Stereochemistry by Tuning the 3,3'-Disubstituents of Phosphoric Acids[J]. J. Am. Chem. Soc.2009,131:15301-15310
[29]a) Jiang J, Yu J, Sun XX, Rao QQ, Gong LZ. Organocatalytic Asymmetric Three-Component Cyclization of Cinnamaldehydes and Primary Amines with 1,3-Dicarbonyl Compounds: Straightforward Access to Enantiomerically Enriched Dihydropyridines[J]. Angew. Chem. Int. Ed. 2008,47:2458-2462. b) Jiang J, Qing J, Gong LZ. Asymmetric Synthesis of 3-Amino-δ-lactams and Benzo[a]quinolizidines by Catalytic Cyclization Reactions Involving Azlactones[J]. Chem. Eur.J.2009,15:7031-7034.
[30]Terada M, Machioka K, Sorimachi K. High Substrate/Catalyst Organocatalysis by a Chiral Br(?)nsted Acid for an Enantioselective Aza-Ene-Type Reaction[J]. Angew. Chem. Int. Ed.2006,45: 2254-2257.
[31]Terada M, Machioka K, Sorimachi K. Chiral Br(?)nsted Acid-Catalyzed Tandem Aza-Ene Type Reaction/Cyclization Cascade for a One-Pot Entry to Enantioenriched Piperidines[J]. J. Am. Chem. Soc.2007,129:10336-10337.
[32]Terada M, Machioka K, Sorimachi K. Activation of Hemiaminal Ethers by Chiral Br(?)nsted Acids for Facile Access to Enantioselective Two-Carbon Homologation Using Enecarbamates[J]. Angew. Chem. Int. Ed.2008,48:2553-2556.
[33]Uraguchi D, Sorimachi K, Terada M. Organocatalytic Asymmetric Direct Alkylation of a-Diazoester via C-H Bond Cleavage[J]..J. Am. Chem. Soc.2005,127:9360-9361.
[34]a) Hashimoto T, Uchiyama N, Maruoka KJ. Trans-Selective Asymmetric Aziridination of Diazoacetamides and N-Boc Imines Catalyzed by Axially Chiral Dicarboxylic Acid[J]. J. Am. Chem. Soc.2008,130:14380-14381. b) Zeng XF, Zeng X, Xu ZJ, Lu M, Zhong GF. Highly Efficient Asymmetric'Trans-Selective Aziridination of Diazoacetamides and N-Boc-imines Catalyzed by Chiral Br(?)nsted Acids[J]. Org. Lett.2009,11:3036-3039. c) Akiyama T, Suzuki T, Mori K. Enantioselective Aza-Darzens Reaction Catalyzed by A Chiral Phosphoric Acid[J]. Org. Lett.2009,11:2445-2447.
[35]a) Akiyama T, Morita H, Itoh J, Fuchibe K. Chiral Br(?)nsted Acid Catalyzed Enantioselective Hydrophosphonylation of Imines:Asymmetric Synthesis of α-Amino Phosphonates[J]. Org. Lett. 2005,7:2583-2585.b) Cheng X, Goddard R, Buth G, List B. Direct Catalytic Asymmetric Three-Component Kabachnik-Fields Reaction[J]. Angew. Chem. Int. Ed.2008,48:5079-5081.
[36]Yue T, Wang MX, Wang DX, Masson G, Zhu JP. Br(?)nsted Acid Catalyzed Enantioselective Three-Component Reaction Involving the α-Addition of Isocyanides to Imines[J]. Angew. Chem. Int. Ed.2009,49:6717-6721.
[37]Rueping M, Antonchick AP. Catalytic Asymmetric Aminoallylation of Aldehydes:A Catalytic Enantioselective Aza-Cope Rearrangement[J]. Angew. Chem. Int. Ed.2008,48: 10090-10093.
[38]a) Rowland GB, Zhang H, Rowland EB, Chennamadhavuni S, Wang Y, Antilla JC. Br(?)nsted Acid-Catalyzed Imine Amidation[J]. J. Am. Chem. Soc.2005,127:15696-15697. b) Cheng X, Vellalath S, Goddard R, List B. Direct Catalytic Asymmetric Synthesis of Cyclic Aminals from Aldehydes[J]. J. Am. Chem. Soc.2008,130:15786-15787. c) Rueping M, Antonchick AP, Sugiono E, Grenader K. Asymmetric Br(?)nsted Acid Catalysis:Catalytic Enantioselective Synthesis of Highly Biologically Active Dihydroquinazolinones[J]. Angew. Chem. Int. Ed.2009, 48:908-910. d) Li G, Fronczek FR, Antilla JC. Catalytic Asymmetric Addition of Alcohols to Imines:Enantioselective Preparation of Chiral N,O-Aminals[J]. J. Am. Chem. Soc.2008,130: 12216-12217.
[39]Miiller S, List B. A Catalytic Asymmetric 6π Electrocyclization:Enantioselective Synthesis of 2-Pyrazolines[J]. Angew. Chem. Int. Ed.2009,48:9975-9978.
[40]Nakashima D, Yamamoto H. Design of Chiral N-Triflyl Phosphoramide as a Strong Chiral Br(?)nsted Acid and Its Application to Asymmetric Diels-Alder Reaction[J]. J. Am. Chem. Soc. 2006,128:9626-9627.
[41]Momiyama N, Tabuse H, Terada M. Chiral Phosphoric Acid-Governed Anti-Diastereoselective and Enantioselective Hetero-Diels-Alder Reaction of Glyoxylate[J]. J. Am. Chem. Soc.2009,131:12882-12883.
[42]Rueping M, Ieawauman W, Antonchick AP, Nachtsheim BJ. Chiral Br(?)nsted Acids in the Catalytic Asymmetric Nazarov Cyclization-The First Enantioselective Organocatalytic Electrocyclic Reaction[J]. Angew. Chem. Int. Ed.2007,46:2097-2100.
[43]Akiyama T, Katoh T, Mori K. Enantioselective Robinson-Type Annulation Reaction Catalyzed by Chiral Phosphoric Acids[J]. Angew. Chem. Int. Ed.2009,48:4226-4228
[44]Mori K, Katoh T, Suzuki T, Noji T, Yamanaka M, Akiyama T. Chiral Phosphoric Acid Catalyzed Desymmetrization of meso-1,3-Diones:Asymmetric Synthesis of Chiral Cyclohexenones[J]. Angew. Chem. Int. Ed.2009,48:9652-9654.
[45]a) Terada M, Soga K, Momiyama N. Enantioselective Activation of Aldehydes by Chiral Phosphoric Acid Catalysts in an Aza-ene-type Reaction between Glyoxylate and Enecarbamate[J]. Angew. Chem.Int. Ed.2008,47:4122-4125. b) Rueping M, Theissmann T, Kuenkel A, Koenigs R M. Highly Enantioselective Organocatalytic Carbonyl-Ene Reaction with Strongly Acidic, Chiral Br(?)nsted Acids as Efficient Catalysts[J]. Angew. Chem. Int. Ed.2008,47:6798-6801.
[46]a) Itoh J, Fuchibe K, Akiyama T. Chiral Phosphoric Acid Catalyzed Enantioselective Friedel-Crafts Alkylation:of Indoles with Nitroalkenes:Cooperative Effect of 3 (?) Molecular Sieves[J]. Angew. Chem. Int. Ed.2008,47:4016-4018. b) Sheng YF, Gu Q, Zhang AJ, You SL. Chiral Bransted Acid-Catalyzed Asymmetric Friedel-Crafts Alkylation of Pyrroles with Nitroolefins[J]. J. Org. Chem.2009,74:6899-6901. c) Sheng YF, Li GQ, Kang Q, Zhang AJ, You SL. Asymmetric Friedel-Crafts Reaction of 4,7-Dihydroindoles with Nitroolefins by Chiral Br(?)nsted Acids under Low Catalyst Loading[J]. Chem. Eur. J.2009,15:3351-3354.
[47]Lu M, Zhu D, Lu YP, Zeng XF, Tan B, Xu ZJ. Zhong GF. Chiral Br(?)nsted Acid-Catalyzed Enantioselective a-Hydroxylation of (3-Dicarbonyl Compounds[J]. J. Am. Chem. Soc.2009,131: 4562-4563.
[48]a) Rowland EB, Rowland GB, Rivera-Otero E, Antilla JC. Br(?)nsted Acid-Catalyzed Desymmetrization of meso-Aziridines[J]. J. Am. Chem. Soc.2007,129:12084-12085. b) Sala G D, Lattanzi A. Highly Enantioselective Synthesis of (3-Amidophenylthioethers by Organocatalytic Desymmetrization of meso-Aziridines[J]. Org. Lett.2009,11:3330-3333. c) Larson S, Baso JC, Li GL, Antilla JC. Chiral Phosphoric Acid-Catalyzed Desymmetrization of meso-Aziridines with Functionalized Mercaptans[J].Org. Lett.2009,11:5186-5189.
[49]Xu SM, Wang Z, Zhang X, Zhang XM, Ding KL. Chiral Br(?)nsted Acid Catalyzed Asymmetric Baeyer-Villiger Reaction of 3-Substituted Cyclobutanones by Using Aqueous H2O2[J]. Angew. Chem. Int. Ed.2008,47:2840-2843
[50]Terada M, Tanaka H, Sorimachi K. Enantioselective Direct Aldol-Type Reaction of Azlactone via Protonation of Vinyl Ethers by a Chiral Br(?)nsted Acid Catalyst[J]. J. Am. Chem. Soc.2009,131:3430-3431.
[51]Zhang QW, Fan CA, Zhang HJ, Tu YQ, Zhao YM, Gu PMM, Chen ZM. Br(?)nsted Acid Catalyzed Enantioselective Semipinacol Rearrangement for the Synthesis of Chiral Spiroethers[J]. Angew. Chem. Int. Ed.2009,48:8572-8574.
[52]a) Sharma V, Crankshaw CL, Piwnica-Worms D. Effects of Multidrug Resistance (MDR1) P-Glycoprotein Expression Levels andCoordination Metal on the Cytotoxic Potency of Multidentate (N4O2)(Ethylenediamine)bis[propyl(R-benzylimino)]metal(III) Cations[J]. J. Med. Chem.1996,39:3483-3490. b) Sage CR, Michelitsch MD, Stout TJ, Biermann D, Nissen R, Finer-Moore J, Stroud R M. D221 in Thymidylate synthase Controls Conformation Change, and Thereby Opening of the Imidazolidine[J]. Biochemistry,1998,37:13893-13901.
[53]a) Viso A, Fernandez de la Pradilla R, Guerrero-Strachan C, Alonso M, Martinez-Ripoll M, Andre I. Sulfur-Directed Asymmetric 1,3-Dipolar Cycloadditions of Azomethine Ylides with Enantiopure Sulinimines[J]. J. Org. Chem.1997,62:2316-2317. b) Viso A, Fernandez de la Pradilla R, Garcia A, Guerrero-Strachan C, Alonso M, Tortosa M, Flores A, Martinez-Ripoll M, Fonseca I, Andre I, Rodriguez A. Highly Diastereoselective [3+2] Cycloadditions between Nonracemic p-Tolylsulfinimines and Iminoesters:An Efficient Entry to Enantiopure Imidazolidines and Vicinal Diaminoalcohols[J]. Chem. Eur. J.2003,9:2867-2876.
[54]Alker D, Harwood LM, Williams CE. Cycloadditions of Aromatic Imines to Enantiomerically Pure Stabilized Azomethine Ylids:Construction of threo (2S,3R)-3-Aryl-2,3-diamino Acids[J]. Tetrahedron Lett.1998,39:475-478.
[55]Chen XH, Zhang WQ, Gong LZ. 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
[56]Chen XH, Wei Q, Luo SW, Xiao H, Gong LZ. Organocatalytic Synthesis of Spiro[pyrrolidin-3,3'-oxindoles] with High Enantiopurity and Structural Diversity[J]. J. Am. Chem. Soc.2009,131:13819-13825
[57]Kitamura M, Tsukamoto M, Bessho Y, Yoshimura M, Kobs U, Widhalm M, Noyori R. Mechanism of Asymmetric Hydrogenation of α-(Acylamino)acrylic Esters Catalyzed by BINAP-Ruthenium(Ⅱ) Diacetate[J]. J. Am. Chem. Soc.2002,124:6649-6667.
[58]Matsunaga S, Das J, Roels J, Vogl EM, Yamamoto N, Iida T, Yamaguchi K, Shibasaki M. 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.
[59]a) Girard C, Kagan HB. Nonlinear Effects in Asymmetric Synthesis and Stereoselective Reactions:Ten Years of Investigation[J]. Angew. Chem. Int. Ed.1998,37:2922-2959. b) Blackmond DG Kinetic Aspects of Nonlinear Effects in Asymmetric Catalysis[J]. Acc. Chem. Res. 2000,33:402-411.
[1]a) Taber DF, He Y. Opening of Aryl-Substituted Epoxides To Form Quaternary Stereogenic Centers:Synthesis of (-)-Mesembrine[J]. J. Org. Chem.2005,70:7711-7714. b) Corey EJ, Xiong Z. Simple Total Synthesis of the Pentacyclic Cs-Symmetric Structure Attributed to the Squalenoid Glabrescol and Three Cs-Symmetric Diastereomers Compel Structural Revision[J]. J. Am. Chem. Soc.2000,122:4831-4832. c) Yamada S, Tsujioka I, Shibatani T, Yoshioka R. Efficient Alternative Synthetic Route to Diltiazem via (2R,3S)-3-(4-Methoxyphenyl)glicidamide[J]. Chem. Pharm. Bull.1999,47:146-150.
[2]a) Bian J, Van Wingerden M, Ready JM. Enantioselective Total Synthesis of (+)- and (-)-Nigellamine A2[J]. J. Am. Chem. Soc.2006,128:7428-7429. b) Gillmore A, Lauret C, Roberts SM. A Route to the Structure Proposed for Puetuberosanol and Approaches to the Natural Products Marshrin and Phebalosin[J]. Tetrahedron 2003,59:4363-4375. c) Piemer B, Hofer O, Greger H. Tryptamine Derived Amides from Cla Usena Indica[J]. Phytochemistry 1997,45: 337-341. d) Milner PH, Coates NJ, Gilpin ML, Spear SR. SB-204900, a Novel Oxirane Carboxamide from Clausena lansium[J]. J. Nat. Prod.1996,59:400-402.
[3]a) Wong OA, Shi Y. Organocatalytic Oxidation. Asymmetric Epoxidation of Olefins Catalyzed by Chiral Ketones and Iminium Salts[J]. Chem. Rev.2008,108:3958-3987. b) Diez D, Nunez M G, Anton AB, Garcia P, Moro RF, Garrido NM, Marcos IS, Basabe P, Urones JG Asymmetric Epoxidation. of Electron-Deficient Olefins[J]. Curr. Org. Synth.2008,5:186-216. c)Michael JP, John S. Asymmetric Epoxidation of Electron-Deficient Olefins[J]. Chem. Commun.2000, 1215-1225.
[4]a) Yamada S, Mashiko T, Terashima S. (Acetylacetonato)[(-)-N-alkylephedrinato]dioxomolyb-denum, a New Class of Chiral Chelate Complexes Which Catalyze Asymmetric Epoxidation of Allylic Alcohol[J]. J. Am. Chem. Soc.,1977,99:1988-1990. b) Michaelson RC, Palermo RE, Sharpless KB. Chiral Hydroxamic Acids as Ligands in the Vanadium Catalyzed Asymmetric Epoxidation of Allylic Alcohols by tert-butyl Hydroperoxide [J]. J. Am. Chem. Soc.,1977,99: 1990-1992.
[5]Jacobsen EN, Zhang W, Muci AR, Ecker JR, Deng L. Highly Enantioselective Epoxidation Catalyst Derived from 1,2-Diaminocyclohexane.J.Am. Chem. Soc.,1991, 113:7063-7064.
[6]Liao SH, List B. Asymmetric Counteranion-Directed Transition-Metal Catalysis: Enantioselective Epoxidation of Alkenes with Manganese(III) Salen Phosphate Complexes[J]. Angew. Chem. Int. Ed.,2009,49:628-631.
[7]Elston CL, Jackson RFW, MacDonald SJF, Murray PJ. Asymmetric Epoxidation of Chalsones with Chiral Modified Lithium and Magnesium tert-Butyl Peroxides [J]. Angew. Chem. Int. Ed., 1997,36:410-412
[8]a) Bougauchi M, Watanabe S, Arai T, Sasai H, Shibasaki M. Catalytic Asymmetric Epoxidation of a,(3-Unsaturated Ketones Promoted by Lanthanoid Complexes. J. Am. Chem. So., 1997,119:2329-2330. b) Watanabe S, Arai T, Sasai H, Bougauchi M, Shibasaki M. The First Catalytic Enantioselective Synthesis of cis-Epoxyketones from cis-Enones. J. Org. Chem.,1998, 63:8090-8091. c) Nemoto T, Ohshima T, Yamaguchi K, Shibasaki M. Catalytic Asymmetric Epoxidation of Enones Using La-BINOL-Triphenylarsine Oxide Complex:Structural Determnation of the Asymmetric Catalyst. J. Am. Chem. So.,2001,123:2725-2732.
[9]Nemoto T, Ohshima T, Shibasaki M. Catalytic Asymmetric Synthesis of α,β-Epoxy Esters, Aldehydes, Amides, and y,δ-Epoxy-β-Keto Esters:Unique Reactivity of α,β-Unsaturated Carbocylic Acid Imidazolides. J. Am. Chem. So.,2001,123:9474-9475.
[10]Nemoto T, Kakei H, Gnanadesikan V, Tosaki SY, Ohshima T, Shibasaki M. Catalytic Asymmetric Epoxidation of a,(3-Unsaturated Amides:Efficient Synthesis of (3-Aryl α-Hydroxy Amides Using a One-Pot Tandem Catalytic Asymmetric Epoxidation-Pd-Catalyzed Epoxide Opening Process. J. Am. Chem. So.,2002,124:14544-14545.
[11]Kakei H, Tsuji R, Ohshima T, Shibasaki M. Catalytic Asymmetric Epoxidation of α,β-Unsaturated Ester Using an Yttrium-Biphenyldiol Complex. J. Am. Chem. So.,2005,127: 8962-8963.
[12]a) Julia S. Masana J, Vega JC. "Synthetic Enzymes" Highly Stereoselective Epoxidation of Chalcone in a Triphasic Toluene- Water-Poly[(S)-alanine] System[J]. Angew. Chem. Int. Ed.,1980, 19:929-931. b) Geller T, Gerlach A, Krtlger CM, Militzer HC. Novel Condition for the Julia-Colonna Epoxidation Reaction Providing Efficient Acess to Chiral, Nonracemic Epoxides[J]. Tetrahedron Lett.,2004, 45:5065-5067. c) Gerlach A, Geller T. Scale-Up Studies for the Asymmetric Julia-Colonna Epoxidation Reaction[J]. Adv. Synth. Catal.2004,346:1247-1249.
[13]a) Lygo B, Wainwright PG. Asymmetric Phase-Transfer Mediated Epoxidation of α,β-Unsaturated Ketone Using Catalysts Derived from Cinchona Alkaloids[J]. Tetrahedron Lett., 1998,39:1599-1602. b) Corey EJ. Zhang FY. Mechanism and Conditions for Highly Enantioselective. Epoxidation of α,β-Enones Using Charge-Accelerated Catalysis by a. Rigid Quaternary Ammonium Salt[J]]Org. Lett.,1999,1:1287-1290. c) Ooi T, Ohara D, Tamura M, Maruka K. Design of New Chiral Phase-Transfer Catalysts with Dual Functions for Highly Enantioselective Epoxidation of α,β-Unsaturated Ketones[J]. J. Am. Chem. Soc.,2004,126: 6844-6845.
[14]a) Lattanzi A. Enantioselective Epoxidation of α,β-Enones Promoted by α,α-Diphenyl-L-prolinol as Bifunctional Organocatalyst[J]. Org. Lett.,2005,7:2579-2582. b) Lattanzi A. Bis(3,5-dimethylphenyl)-(S)-pyrrolidin-2-ylmethanol:an Improved Organocatalyst for Asymmetric Epoxidation of α,β-Enones[J]. Adv. Synth. Catal.2006,348:339-346. c) Li YW, Liu XY, Yang YQ, Zhao G.4-Substituted-α,α-diaryl-prolinols Improve the Enantioselective Catalytic Epoxidation of α,β-Enones[J]. J. Org. Chem.,2007,72:288-291.
[15]a) Marigo M, Johan F, Poulsen TB, Zhuang W, Jorgensen KA. Asymmetric Organocatalytic Epoxidation of α,β-Unsaturated Aldehydes with Hydrogen Peroxide[J]. J. Am. Chem. Soc.,2005, 127:6964-6965. b) Wang XW, List B. Asymmetric Counteranion-Directed Catalysis for the Epoxidation of Enals[J]. Angew. Chem. Int. Ed.,2007,47:1119-1122.
[16]Wang XW, Reisinger CM, List B. Catalytic Asymmetric Epoxidation of Cyclic Enones[J]. J. Am. Chem. Soc.,2008,130:6070-6071.
[17]Wu XY, She XG, Shi YA.Highly Enantioselective Epoxidation of α,β-Unsaturated Esters by Chiral Dioxirane[J].J. Am. Chem. Soc.,2002,124:8792-8793.
[18]a) Arai S, Shioiri T. Catalytic Asymmetric Darzens Condensation Under Phase-Transfer-Catalyzed Conditions[J]. Tetrahedron Lett.,1998,39:2145-2148. b) Bako P, Vizardi K, Bajorm Z, Toke L. Synthesis and Application in Asymmetric Synthesis of Azacrown Ethers Derived from D-Glucose[J]. Chem. Commun.1998,1193-1195. c) Bako P, Czinege E, Bako T, Czugler M, Toke L. Asymmetric C-C Bond Forming Reaction with Chiral Crown Catalysts Derived from D-Glucose and D-Galactose[J].Tetrahedron:Asymmetry 1999,10: 4539-4551
[19]Arai S, Shirai Y, Ishida T, Shioiri T. Phase-Transfer Catalyzed Asymmetric Darzens Reaction of Cyclic a-Chloro Ketones[J]. Chem. Commun.1999,49-50
[20]Arai S, Shioiri T. Asymmetric Darzens Reaction Utilizing Chloromethyl Phenyl Sulfone Under Phase-Transfer Catalyzed Conditions[J]. Tetrahedron 2002,58:1407-1413.
[21]a) Arai S, Tokumaru K, Aoyama T. Phase-Transfer Catalyzed Asymmetric Darzens Reaction Using a New Chiral Ammonium Salt[J]. Tetrahedron Lett.,2004,45:1845-1848.b) Achard TJR, Belokon YN, Ilyin M, Moskalenko M, North M, Pizzato F. Enantio-and Diastereoselective Darzens Condensations[J]. Tetrahedron Lett.,2007,48:2965-2969.
[22]Imashiro R, Yamanaka T, Seki M. Catalytic Asymmetric Synthesis of Glycidic Amides via Chiral Sulfur Ylides[J]. Tetrahedron:Asymmetry,1999,10:2845-2851.
[23]a) Aggarwal VK, Hynd G, Picoul W, Vasse, JL. Highly Enantioselective Darzens Reaction of a Camphor-Derived Sulfonium Amide to Give Glycidic Amides and Their Applications in Synthesis[J]. J. Am. Chem. Soc.,2002,124:9964-9965; b) Aggarwal VK, Charmant JPH, Fuentes D, Harvey JN, Hynd G, Ohara D, Picoul W, Smith C, Vasse J L, Winn C L. Highly Enantioselective Synthesis of Glycidic Amides Using Camphor-Derived Sulfonium Salts. Mechanism and Applications in Synthesis[J]. J. Am. Chem. Soc.2006,128:2105-2114.
[24]a) Guchi D, Sorimachi K, Terada M. Organocatalytic Asymmetric Direct Alkylation of a-Diazoester via C-H Bond Cleavage[J]. J. Am. Chem. Soc.2005,127:9360-9361. b) imoto T, Maruoka K.. Design of Chiral Dicarboxylic Acid for Asymmetric Mannich Reaction of Arylaldehyde N-Boc Imines and Diazo Compound[J]. J. Am. Chem. Soc.2007,129: 10054-10055.
[25]Hashimoto T, Uchiyama N, Maruoka KJ. Trans-Selective Asymmetric Aziridination of Diazoacetamides and N-Boc Imines Catalyzed by Axially Chiral Dicarboxylic Acid[J]. J. Am. Chem. Soc.2008,130:14380-14381.
[26]a) Yao WG, Wang JB. Direct Catalytic Asymmetric Aldol-Type Reaction of Aldehydes with Ethyl Diazoacetate[J]. Org. Lett.2003,5:1527-1530. b) Trost BM, Malhotra S, Fried BA. Magnesium-Catalyze Asymmetric Direct Aldol Addition of Ethyl Diazoacetate to Aromatic, Aliphatic, and α,β-Unsaturated Aldehydes[J]. J. Am. Chem. Soc.2009,131:1674-1675.
[27]a) Tony KMS, To L, Lee M, Chi ML. Asymmetric epoxidation of cis-alkenes with arabinose-derived ketones:enantioselective synthesis of the side chain of Taxol[J]. Tetrahedron 2006,62:6621-6629. b) Feske BD, Stewart JD. Chemoenzymatic formal total synthesis of (-)-bestatin[J]. Tetrahedron:Asymmetry 2005,16:3124-3127.
[28]a) Zhang Y, Desai A, Lu Z, Hu G, Ding Z, Wuff WD. Catalytic Asymmetric Aziridination with Borate Catalysts Derived from VANOL and VAPOL Ligands:Scope and Mechanistic Studies [J]. Chem. Eur. J.2008,14:3785-3803. b) Casarrubios L, Perez JA, Brookhart M, Templeton JL. Lewis Acid-Catalyzed Synthesis of Aziridines [J]. J. Org. Chem 1996,61:8358-8359.
[2]尤启东,林国强.2003.手性药物-研究与应用：化学工业出版社.
[3]Bredig G, Fiske WS, Biochem Z 1912,7
[4]List B, Lerner R A, Barbas III CF. Proline-Catalyzed Direct Asymmetric Aldol Reactions[J]. J. Am. Chem. Soc.,2000,122:2395-2396.
[5]Ahrendt K A, Borths C J, MacMillan DWC. New Strategies for Organic Catalysis:The First Highly Enantioselective Organocatalytic Diels-Alder Reaction[J]. J. Am. Chem. So.,2000,122: 4243-4244.
[6]Mukherjee S, Yang JW, Hoffmann S, List B. Asymmetric Enamine Catalysis[J]. Chem. Rev., 2007,107:5471-5569.
[7]Erkkila A, Majander I, Pihko PM. Iminium Catalysis[J]. Chem. Rev.,2007,107:5416-5470.
[8]Doyle A G, Jacobsen E N. Small-Molecule H-Bond Donors in Asymmetric Catalysis[J]. Chem. Rev.,2007,107:5713-5743.
[9]a) Akiyama T. Stronger Br(?)nsted acids[J]. Chem. Rev.,2007,107:5744-5758. b) Terada M. Binaphthol-derived phosphoric acid as a versatile catalyst for enantioselective carbon-carbon bond forming reactions[J]. Chem. Commun.2008,4097-4112.
[10]Hashimoto T, Maruoka KJ. Recent Development and Application of Chiral Phase-Transfer Catalysts[J]. Chem. Rev.,2007,107:5656-5682.
[11]Enders D, Niemeier O, Henseler A. Organocatalysis by N-Heterocyclic Carbenes[J]. Chem. Rev.,2007,107:5606-5655.
[12]a) Kobayashi S, Ishitani H. Catalytic Enantioselective Addition to Imines[J]. Chem. Rev., 1999,99:1069-1094. b) Johnson JS, Evans DA. Chiral Bis(oxazoline) Copper(Ⅱ) Complexes: Versatile Catalysts for Enantioselective Cycloaddition, Aldol, Michael, and Carbonyl Ene Reactions[J]. Acc. Chem. Res.,2000,33:325-335.
[13]a) Sigman MS, Jacobsen EN. Schiff Base Catalysts for the Asymmetric Strecker Reaction Identified and Optimized from Parallel Synthetic Libraries[J]. J. Am. Chem. Soc.1998,120: 4901-4902. b) Huang Y, Unni AK, Thadani AN, Rawal VH. Hydrogen Bonding:Single Enantiomers from a Chiral-alcohol Catalyst[J]. Nature 2003,424:146-146.
[14]a) Akiyama T, Itoh J, Yokota K, Fuchibe K. Enantioselective Mannich-Type Reaction Catalyzed by a Chiral Br(?)nsted Acid[J]. Angew.. Chem. Int. Ed.,2004,43:1566-1568. b) Yamanaka M, Itoh J, Fuchibe K, Akiyama T. Chiral Br(?)nsted Acid Catalyzed Enantioselective Mannich-Type Reaction[J]. J. Am. Chem. Soc.2007,129:6756-6764. c) Uraguchi D,Terada M. Chiral Br(?)nsted Acid-Catalyzed Direct Mannich Reactions via Electrophilic Activation[J]. J. Am. Chem. Soc.2004,126:5356-5357.
[15]Guo QX, Liu H, Guo C, Luo SW, Gu Y, Gong LZ. Chiral Br(?)nsted Acid-Catalyzed Direct Asymmetric Mannich Reaction[J]. J. Am. Chem. Soc.2007,129:3790-379.
[16]a) Sickert M, Schneider C. The Enantioselective, Br(?)nsted Acid-Catalyzed, Vinylogous Mannich Reaction[J]. Angew. Chem. Int. Ed.2008,47:3631-3634. b) Giera DS, Sickert M, Schneider C. Br(?)nsted Acid-Catalyzed, Enantioselective, Vinylogous Mannich Reaction of Vinylketene Silyl N,O-Acetals[J]. Org. Lett.2008,10:4259-4262.
[17]Uraguchi D, Sorimachi K, Terada M. Organocatalytic Asymmetric Aza-Friedel-Crafts Alkylation of Furan[J]. J. Am. Chem. Soc.2004,126:11804-11805.
[18]a) Terada M, Sorimachi K. Enantioselective Friedel-Crafts Reaction of Electron-Rich Alkenes Catalyzed by Chiral Br(?)nsted Acid[J]. J. Am. Chem. Soc.2007,129:292-293. b) Jia YX, Zhong J, Zhu SF, Zhang CM, Zhou QL. Chiral Br(?)nsted Acid Catalyzed Enantioselective Friedel-Crafts Reaction of Indoles and a-Aryl Enamides:Construction of Quaternary Carbon Atoms[J]. Angew. Chem. Int. Ed.2007,46:5565-5567. c) Kang Q, Zhao ZA, You SL. Highly Enantioselective Friedel-Crafts Reaction of Indoles with Imines by a Chiral Phosphoric Acid[J]. J. Am. Chem. Soc.2007,129:1484-1485.
[19]a) Seayad J, Seayad AM, List B. Catalytic Asymmetric Pictet-Spengler Reaction[J]. J. Am. Chem. Soc. 2006,128:1086-1087. b) Wanner M J, Haas R, Cuba.K, Maarseveen J, Hiemstra H. Catalytic Asymmetric Pictet-Spengler Reactions via Sulfenyliminium Ions[J]. Angew. Chem. Int. Ed.2007,46:7485-7487.
[20]Muratore ME, Holloway C A, Pilling A, Storer RI, Trevitt G, Dixon DJ. Enantioselective Br(?)nsted Acid-Catalyzed N-Acyliminium Cyclization Cascades[J]. J. Am. Chem. Soc.2009,131: 10796-10797.
[21]Akiyama T, Itoh J, Fuchibe K. Chiral Br(?)nsted Acid Catalyzed Enantioselective Aza-Diels-Alder Reaction of Brassard's Diene with Imines[J]. Angew. Chem. Int. Ed.2006,45: 4796-4798.
[22]a) Akiyama T, Morita H, Fuchibe K. Chiral Br(?)nsted Acid-Catalyzed Inverse Electron-Demand Aza Diels-Alder Reaction[J]. J. Am. Chem. Soc.2006,128:13070-13071. b) Liu H, Dagousset G, Masson G, Retailleau P, Zhu JP. Chiral Br(?)nsted Acid-Catalyzed Enantioselective Three-Component Pavarov Reaction[J]. J. Am. Chem. Soc.2009,131: 4598-4599.
[23]a) Liu H, Cun LF, Mi AQ, Jiang YZ, Gong LZ. Enantioselective Direct Aza Hetero-Diels-Alder Reaction Catalyzed by Chiral Br(?)nsted Acids[J]. Org. Lett.2006,8: 6023-6026. b) Rueping, M.; Azap,C.; Effective Interplay of Two Br(?)nsted Acids in the Asymmetric Synthesis of Isoquinuclidines[J]. Angew. Chem. Int. Ed.2006,45:7832-7835.
[24]a) Rueping M, Sugiono E, Azap C, Theissmann T, Bolte M. Enantioselective Br(?)nsted Acid Catalyzed Transfer Hydrogenation:Organocatalytic Reduction of Imines[J]. Org.Lett.2005,7: 3781-3783. b) Hoffmann S, Seayad A M, List B. A Powerful Br(?)nsted Acid Catalyst for the Organocatalytic Asymmetric Transfer Hydrogenation of Imines[J]. Angew.Chem., Int. Ed.2005, 44:7424-7427. c) Storer RI, Carrera DE, Ni Y, MacMillan DWC. Enantioselective Organocatalytic Reductive Amination[J]. J. Am. Chem. Soc.2006,128:84-86. d) Li G, Liang Y, Antilla JC. A Vaulted Biaryl Phosphoric Acid-Catalyzed Reduction of a-Imino Esters:The Highly Enantioselective Preparation of a-Amino Esters[J]. J. Am. Chem. Soc.2007,129: 5830-5831. e) Kang Q, Zhao ZA, You SL. Highly Enantioselective Transfer Hydrogenation of a-Imino Esters by a Phosphoric Acid[J]. Adv. Synth. Catal.2007,349:1657-1660. f) Kang Q, Zhao ZA, You SL. Asymmetric Transfer Hydrogenation of β,γ-Alkynyl a-Imino Esters by a Br(?)nsted Acid[J].Org. Lett.2008,10:2031-2034.
[25]a) Rueping M, Antonchick AP, Theissmann T. A Highly Enantioselective Br(?)nsted Acid Catalyzed Cascade Reaction:Organocatalytic Transfer Hydrogenation of Quinolines and their Application in the Synthesis of Alkaloids[J]. Angew. Chem., Int. Ed.2006,45:3683-3686. b) Rueping M, Antonchick AP, Theissmann T. Remarkably Low Catalyst Loading in Br(?)nsted Acid Catalyzed Transfer Hydrogenations:Enantioselective Reduction of Benzoxazines, Benzothiazines, and Benzoxazinones[J]. Angew. Chem., Int. Ed.2006,45:6751-6755.
[26]a) Mayer S, List B. Asymmetric Counteranion-Directed Catalysis[J]. Angew. Chem. Int. Ed. 2006,45:4193-4195. b) Yang JW, Hechavarria Fonseca MT, Vignola N, List B. Metal-Free, Organocatalytic Asymmetric Transfer Hydrogenation of a,β-unsaturated Aldehydes[J]. Angew. Chem. Int. Ed.2005,44:108-110. c) Ouellet S. G, Tuttle JB, MacMillan DWC. Enantioselective Organocatalytic Hydride Reduction[J]. J. Am. Chem. Soc.2005,127:32-33. d) Martin NJA, List B. Highly Enantioselective Transfer Hydrogenation of α,β-Unsaturated Ketones[J]. J. Am. Chem. Soc.2006,128:13368-13369.
[27]Hoffmann S, Nicoletti M, List B. Catalytic Asymmetric Reductive Amination of Aldehydes via Dynamic Kinetic Resolution[J]. J. Am. Chem. Soc.2006,128:13074-13075.
[28]a) Chen XH, Xu XY, LiuH, Cun LF, Gong LZ. Highly Enantioselective Organocatalytic Biginelli Reaction[J]. J. Am. Chem. Soc.2006,128:14802-14803. b) Li N, Chen XH, Song J, Luo SW, Fan W. Gong LZ. Highly Enantioselective Organocatalytic Biginelli and Biginelli-Like Condensations:Reversal of the Stereochemistry by Tuning the 3,3'-Disubstituents of Phosphoric Acids[J]. J. Am. Chem. Soc.2009,131:15301-15310
[29]a) Jiang J, Yu J, Sun XX, Rao QQ, Gong LZ. Organocatalytic Asymmetric Three-Component Cyclization of Cinnamaldehydes and Primary Amines with 1,3-Dicarbonyl Compounds: Straightforward Access to Enantiomerically Enriched Dihydropyridines[J]. Angew. Chem. Int. Ed. 2008,47:2458-2462. b) Jiang J, Qing J, Gong LZ. Asymmetric Synthesis of 3-Amino-δ-lactams and Benzo[a]quinolizidines by Catalytic Cyclization Reactions Involving Azlactones[J]. Chem. Eur.J.2009,15:7031-7034.
[30]Terada M, Machioka K, Sorimachi K. High Substrate/Catalyst Organocatalysis by a Chiral Br(?)nsted Acid for an Enantioselective Aza-Ene-Type Reaction[J]. Angew. Chem. Int. Ed.2006,45: 2254-2257.
[31]Terada M, Machioka K, Sorimachi K. Chiral Br(?)nsted Acid-Catalyzed Tandem Aza-Ene Type Reaction/Cyclization Cascade for a One-Pot Entry to Enantioenriched Piperidines[J]. J. Am. Chem. Soc.2007,129:10336-10337.
[32]Terada M, Machioka K, Sorimachi K. Activation of Hemiaminal Ethers by Chiral Br(?)nsted Acids for Facile Access to Enantioselective Two-Carbon Homologation Using Enecarbamates[J]. Angew. Chem. Int. Ed.2008,48:2553-2556.
[33]Uraguchi D, Sorimachi K, Terada M. Organocatalytic Asymmetric Direct Alkylation of a-Diazoester via C-H Bond Cleavage[J]..J. Am. Chem. Soc.2005,127:9360-9361.
[34]a) Hashimoto T, Uchiyama N, Maruoka KJ. Trans-Selective Asymmetric Aziridination of Diazoacetamides and N-Boc Imines Catalyzed by Axially Chiral Dicarboxylic Acid[J]. J. Am. Chem. Soc.2008,130:14380-14381. b) Zeng XF, Zeng X, Xu ZJ, Lu M, Zhong GF. Highly Efficient Asymmetric'Trans-Selective Aziridination of Diazoacetamides and N-Boc-imines Catalyzed by Chiral Br(?)nsted Acids[J]. Org. Lett.2009,11:3036-3039. c) Akiyama T, Suzuki T, Mori K. Enantioselective Aza-Darzens Reaction Catalyzed by A Chiral Phosphoric Acid[J]. Org. Lett.2009,11:2445-2447.
[35]a) Akiyama T, Morita H, Itoh J, Fuchibe K. Chiral Br(?)nsted Acid Catalyzed Enantioselective Hydrophosphonylation of Imines:Asymmetric Synthesis of α-Amino Phosphonates[J]. Org. Lett. 2005,7:2583-2585.b) Cheng X, Goddard R, Buth G, List B. Direct Catalytic Asymmetric Three-Component Kabachnik-Fields Reaction[J]. Angew. Chem. Int. Ed.2008,48:5079-5081.
[36]Yue T, Wang MX, Wang DX, Masson G, Zhu JP. Br(?)nsted Acid Catalyzed Enantioselective Three-Component Reaction Involving the α-Addition of Isocyanides to Imines[J]. Angew. Chem. Int. Ed.2009,49:6717-6721.
[37]Rueping M, Antonchick AP. Catalytic Asymmetric Aminoallylation of Aldehydes:A Catalytic Enantioselective Aza-Cope Rearrangement[J]. Angew. Chem. Int. Ed.2008,48: 10090-10093.
[38]a) Rowland GB, Zhang H, Rowland EB, Chennamadhavuni S, Wang Y, Antilla JC. Br(?)nsted Acid-Catalyzed Imine Amidation[J]. J. Am. Chem. Soc.2005,127:15696-15697. b) Cheng X, Vellalath S, Goddard R, List B. Direct Catalytic Asymmetric Synthesis of Cyclic Aminals from Aldehydes[J]. J. Am. Chem. Soc.2008,130:15786-15787. c) Rueping M, Antonchick AP, Sugiono E, Grenader K. Asymmetric Br(?)nsted Acid Catalysis:Catalytic Enantioselective Synthesis of Highly Biologically Active Dihydroquinazolinones[J]. Angew. Chem. Int. Ed.2009, 48:908-910. d) Li G, Fronczek FR, Antilla JC. Catalytic Asymmetric Addition of Alcohols to Imines:Enantioselective Preparation of Chiral N,O-Aminals[J]. J. Am. Chem. Soc.2008,130: 12216-12217.
[39]Miiller S, List B. A Catalytic Asymmetric 6π Electrocyclization:Enantioselective Synthesis of 2-Pyrazolines[J]. Angew. Chem. Int. Ed.2009,48:9975-9978.
[40]Nakashima D, Yamamoto H. Design of Chiral N-Triflyl Phosphoramide as a Strong Chiral Br(?)nsted Acid and Its Application to Asymmetric Diels-Alder Reaction[J]. J. Am. Chem. Soc. 2006,128:9626-9627.
[41]Momiyama N, Tabuse H, Terada M. Chiral Phosphoric Acid-Governed Anti-Diastereoselective and Enantioselective Hetero-Diels-Alder Reaction of Glyoxylate[J]. J. Am. Chem. Soc.2009,131:12882-12883.
[42]Rueping M, Ieawauman W, Antonchick AP, Nachtsheim BJ. Chiral Br(?)nsted Acids in the Catalytic Asymmetric Nazarov Cyclization-The First Enantioselective Organocatalytic Electrocyclic Reaction[J]. Angew. Chem. Int. Ed.2007,46:2097-2100.
[43]Akiyama T, Katoh T, Mori K. Enantioselective Robinson-Type Annulation Reaction Catalyzed by Chiral Phosphoric Acids[J]. Angew. Chem. Int. Ed.2009,48:4226-4228
[44]Mori K, Katoh T, Suzuki T, Noji T, Yamanaka M, Akiyama T. Chiral Phosphoric Acid Catalyzed Desymmetrization of meso-1,3-Diones:Asymmetric Synthesis of Chiral Cyclohexenones[J]. Angew. Chem. Int. Ed.2009,48:9652-9654.
[45]a) Terada M, Soga K, Momiyama N. Enantioselective Activation of Aldehydes by Chiral Phosphoric Acid Catalysts in an Aza-ene-type Reaction between Glyoxylate and Enecarbamate[J]. Angew. Chem.Int. Ed.2008,47:4122-4125. b) Rueping M, Theissmann T, Kuenkel A, Koenigs R M. Highly Enantioselective Organocatalytic Carbonyl-Ene Reaction with Strongly Acidic, Chiral Br(?)nsted Acids as Efficient Catalysts[J]. Angew. Chem. Int. Ed.2008,47:6798-6801.
[46]a) Itoh J, Fuchibe K, Akiyama T. Chiral Phosphoric Acid Catalyzed Enantioselective Friedel-Crafts Alkylation:of Indoles with Nitroalkenes:Cooperative Effect of 3 (?) Molecular Sieves[J]. Angew. Chem. Int. Ed.2008,47:4016-4018. b) Sheng YF, Gu Q, Zhang AJ, You SL. Chiral Bransted Acid-Catalyzed Asymmetric Friedel-Crafts Alkylation of Pyrroles with Nitroolefins[J]. J. Org. Chem.2009,74:6899-6901. c) Sheng YF, Li GQ, Kang Q, Zhang AJ, You SL. Asymmetric Friedel-Crafts Reaction of 4,7-Dihydroindoles with Nitroolefins by Chiral Br(?)nsted Acids under Low Catalyst Loading[J]. Chem. Eur. J.2009,15:3351-3354.
[47]Lu M, Zhu D, Lu YP, Zeng XF, Tan B, Xu ZJ. Zhong GF. Chiral Br(?)nsted Acid-Catalyzed Enantioselective a-Hydroxylation of (3-Dicarbonyl Compounds[J]. J. Am. Chem. Soc.2009,131: 4562-4563.
[48]a) Rowland EB, Rowland GB, Rivera-Otero E, Antilla JC. Br(?)nsted Acid-Catalyzed Desymmetrization of meso-Aziridines[J]. J. Am. Chem. Soc.2007,129:12084-12085. b) Sala G D, Lattanzi A. Highly Enantioselective Synthesis of (3-Amidophenylthioethers by Organocatalytic Desymmetrization of meso-Aziridines[J]. Org. Lett.2009,11:3330-3333. c) Larson S, Baso JC, Li GL, Antilla JC. Chiral Phosphoric Acid-Catalyzed Desymmetrization of meso-Aziridines with Functionalized Mercaptans[J].Org. Lett.2009,11:5186-5189.
[49]Xu SM, Wang Z, Zhang X, Zhang XM, Ding KL. Chiral Br(?)nsted Acid Catalyzed Asymmetric Baeyer-Villiger Reaction of 3-Substituted Cyclobutanones by Using Aqueous H2O2[J]. Angew. Chem. Int. Ed.2008,47:2840-2843
[50]Terada M, Tanaka H, Sorimachi K. Enantioselective Direct Aldol-Type Reaction of Azlactone via Protonation of Vinyl Ethers by a Chiral Br(?)nsted Acid Catalyst[J]. J. Am. Chem. Soc.2009,131:3430-3431.
[51]Zhang QW, Fan CA, Zhang HJ, Tu YQ, Zhao YM, Gu PMM, Chen ZM. Br(?)nsted Acid Catalyzed Enantioselective Semipinacol Rearrangement for the Synthesis of Chiral Spiroethers[J]. Angew. Chem. Int. Ed.2009,48:8572-8574.
[52]a) Sharma V, Crankshaw CL, Piwnica-Worms D. Effects of Multidrug Resistance (MDR1) P-Glycoprotein Expression Levels andCoordination Metal on the Cytotoxic Potency of Multidentate (N4O2)(Ethylenediamine)bis[propyl(R-benzylimino)]metal(III) Cations[J]. J. Med. Chem.1996,39:3483-3490. b) Sage CR, Michelitsch MD, Stout TJ, Biermann D, Nissen R, Finer-Moore J, Stroud R M. D221 in Thymidylate synthase Controls Conformation Change, and Thereby Opening of the Imidazolidine[J]. Biochemistry,1998,37:13893-13901.
[53]a) Viso A, Fernandez de la Pradilla R, Guerrero-Strachan C, Alonso M, Martinez-Ripoll M, Andre I. Sulfur-Directed Asymmetric 1,3-Dipolar Cycloadditions of Azomethine Ylides with Enantiopure Sulinimines[J]. J. Org. Chem.1997,62:2316-2317. b) Viso A, Fernandez de la Pradilla R, Garcia A, Guerrero-Strachan C, Alonso M, Tortosa M, Flores A, Martinez-Ripoll M, Fonseca I, Andre I, Rodriguez A. Highly Diastereoselective [3+2] Cycloadditions between Nonracemic p-Tolylsulfinimines and Iminoesters:An Efficient Entry to Enantiopure Imidazolidines and Vicinal Diaminoalcohols[J]. Chem. Eur. J.2003,9:2867-2876.
[54]Alker D, Harwood LM, Williams CE. Cycloadditions of Aromatic Imines to Enantiomerically Pure Stabilized Azomethine Ylids:Construction of threo (2S,3R)-3-Aryl-2,3-diamino Acids[J]. Tetrahedron Lett.1998,39:475-478.
[55]Chen XH, Zhang WQ, Gong LZ. 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
[56]Chen XH, Wei Q, Luo SW, Xiao H, Gong LZ. Organocatalytic Synthesis of Spiro[pyrrolidin-3,3'-oxindoles] with High Enantiopurity and Structural Diversity[J]. J. Am. Chem. Soc.2009,131:13819-13825
[57]Kitamura M, Tsukamoto M, Bessho Y, Yoshimura M, Kobs U, Widhalm M, Noyori R. Mechanism of Asymmetric Hydrogenation of α-(Acylamino)acrylic Esters Catalyzed by BINAP-Ruthenium(Ⅱ) Diacetate[J]. J. Am. Chem. Soc.2002,124:6649-6667.
[58]Matsunaga S, Das J, Roels J, Vogl EM, Yamamoto N, Iida T, Yamaguchi K, Shibasaki M. 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.
[59]a) Girard C, Kagan HB. Nonlinear Effects in Asymmetric Synthesis and Stereoselective Reactions:Ten Years of Investigation[J]. Angew. Chem. Int. Ed.1998,37:2922-2959. b) Blackmond DG Kinetic Aspects of Nonlinear Effects in Asymmetric Catalysis[J]. Acc. Chem. Res. 2000,33:402-411.
[1]a) Taber DF, He Y. Opening of Aryl-Substituted Epoxides To Form Quaternary Stereogenic Centers:Synthesis of (-)-Mesembrine[J]. J. Org. Chem.2005,70:7711-7714. b) Corey EJ, Xiong Z. Simple Total Synthesis of the Pentacyclic Cs-Symmetric Structure Attributed to the Squalenoid Glabrescol and Three Cs-Symmetric Diastereomers Compel Structural Revision[J]. J. Am. Chem. Soc.2000,122:4831-4832. c) Yamada S, Tsujioka I, Shibatani T, Yoshioka R. Efficient Alternative Synthetic Route to Diltiazem via (2R,3S)-3-(4-Methoxyphenyl)glicidamide[J]. Chem. Pharm. Bull.1999,47:146-150.
[2]a) Bian J, Van Wingerden M, Ready JM. Enantioselective Total Synthesis of (+)- and (-)-Nigellamine A2[J]. J. Am. Chem. Soc.2006,128:7428-7429. b) Gillmore A, Lauret C, Roberts SM. A Route to the Structure Proposed for Puetuberosanol and Approaches to the Natural Products Marshrin and Phebalosin[J]. Tetrahedron 2003,59:4363-4375. c) Piemer B, Hofer O, Greger H. Tryptamine Derived Amides from Cla Usena Indica[J]. Phytochemistry 1997,45: 337-341. d) Milner PH, Coates NJ, Gilpin ML, Spear SR. SB-204900, a Novel Oxirane Carboxamide from Clausena lansium[J]. J. Nat. Prod.1996,59:400-402.
[3]a) Wong OA, Shi Y. Organocatalytic Oxidation. Asymmetric Epoxidation of Olefins Catalyzed by Chiral Ketones and Iminium Salts[J]. Chem. Rev.2008,108:3958-3987. b) Diez D, Nunez M G, Anton AB, Garcia P, Moro RF, Garrido NM, Marcos IS, Basabe P, Urones JG Asymmetric Epoxidation. of Electron-Deficient Olefins[J]. Curr. Org. Synth.2008,5:186-216. c)Michael JP, John S. Asymmetric Epoxidation of Electron-Deficient Olefins[J]. Chem. Commun.2000, 1215-1225.
[4]a) Yamada S, Mashiko T, Terashima S. (Acetylacetonato)[(-)-N-alkylephedrinato]dioxomolyb-denum, a New Class of Chiral Chelate Complexes Which Catalyze Asymmetric Epoxidation of Allylic Alcohol[J]. J. Am. Chem. Soc.,1977,99:1988-1990. b) Michaelson RC, Palermo RE, Sharpless KB. Chiral Hydroxamic Acids as Ligands in the Vanadium Catalyzed Asymmetric Epoxidation of Allylic Alcohols by tert-butyl Hydroperoxide [J]. J. Am. Chem. Soc.,1977,99: 1990-1992.
[5]Jacobsen EN, Zhang W, Muci AR, Ecker JR, Deng L. Highly Enantioselective Epoxidation Catalyst Derived from 1,2-Diaminocyclohexane.J.Am. Chem. Soc.,1991, 113:7063-7064.
[6]Liao SH, List B. Asymmetric Counteranion-Directed Transition-Metal Catalysis: Enantioselective Epoxidation of Alkenes with Manganese(III) Salen Phosphate Complexes[J]. Angew. Chem. Int. Ed.,2009,49:628-631.
[7]Elston CL, Jackson RFW, MacDonald SJF, Murray PJ. Asymmetric Epoxidation of Chalsones with Chiral Modified Lithium and Magnesium tert-Butyl Peroxides [J]. Angew. Chem. Int. Ed., 1997,36:410-412
[8]a) Bougauchi M, Watanabe S, Arai T, Sasai H, Shibasaki M. Catalytic Asymmetric Epoxidation of a,(3-Unsaturated Ketones Promoted by Lanthanoid Complexes. J. Am. Chem. So., 1997,119:2329-2330. b) Watanabe S, Arai T, Sasai H, Bougauchi M, Shibasaki M. The First Catalytic Enantioselective Synthesis of cis-Epoxyketones from cis-Enones. J. Org. Chem.,1998, 63:8090-8091. c) Nemoto T, Ohshima T, Yamaguchi K, Shibasaki M. Catalytic Asymmetric Epoxidation of Enones Using La-BINOL-Triphenylarsine Oxide Complex:Structural Determnation of the Asymmetric Catalyst. J. Am. Chem. So.,2001,123:2725-2732.
[9]Nemoto T, Ohshima T, Shibasaki M. Catalytic Asymmetric Synthesis of α,β-Epoxy Esters, Aldehydes, Amides, and y,δ-Epoxy-β-Keto Esters:Unique Reactivity of α,β-Unsaturated Carbocylic Acid Imidazolides. J. Am. Chem. So.,2001,123:9474-9475.
[10]Nemoto T, Kakei H, Gnanadesikan V, Tosaki SY, Ohshima T, Shibasaki M. Catalytic Asymmetric Epoxidation of a,(3-Unsaturated Amides:Efficient Synthesis of (3-Aryl α-Hydroxy Amides Using a One-Pot Tandem Catalytic Asymmetric Epoxidation-Pd-Catalyzed Epoxide Opening Process. J. Am. Chem. So.,2002,124:14544-14545.
[11]Kakei H, Tsuji R, Ohshima T, Shibasaki M. Catalytic Asymmetric Epoxidation of α,β-Unsaturated Ester Using an Yttrium-Biphenyldiol Complex. J. Am. Chem. So.,2005,127: 8962-8963.
[12]a) Julia S. Masana J, Vega JC. "Synthetic Enzymes" Highly Stereoselective Epoxidation of Chalcone in a Triphasic Toluene- Water-Poly[(S)-alanine] System[J]. Angew. Chem. Int. Ed.,1980, 19:929-931. b) Geller T, Gerlach A, Krtlger CM, Militzer HC. Novel Condition for the Julia-Colonna Epoxidation Reaction Providing Efficient Acess to Chiral, Nonracemic Epoxides[J]. Tetrahedron Lett.,2004, 45:5065-5067. c) Gerlach A, Geller T. Scale-Up Studies for the Asymmetric Julia-Colonna Epoxidation Reaction[J]. Adv. Synth. Catal.2004,346:1247-1249.
[13]a) Lygo B, Wainwright PG. Asymmetric Phase-Transfer Mediated Epoxidation of α,β-Unsaturated Ketone Using Catalysts Derived from Cinchona Alkaloids[J]. Tetrahedron Lett., 1998,39:1599-1602. b) Corey EJ. Zhang FY. Mechanism and Conditions for Highly Enantioselective. Epoxidation of α,β-Enones Using Charge-Accelerated Catalysis by a. Rigid Quaternary Ammonium Salt[J]]Org. Lett.,1999,1:1287-1290. c) Ooi T, Ohara D, Tamura M, Maruka K. Design of New Chiral Phase-Transfer Catalysts with Dual Functions for Highly Enantioselective Epoxidation of α,β-Unsaturated Ketones[J]. J. Am. Chem. Soc.,2004,126: 6844-6845.
[14]a) Lattanzi A. Enantioselective Epoxidation of α,β-Enones Promoted by α,α-Diphenyl-L-prolinol as Bifunctional Organocatalyst[J]. Org. Lett.,2005,7:2579-2582. b) Lattanzi A. Bis(3,5-dimethylphenyl)-(S)-pyrrolidin-2-ylmethanol:an Improved Organocatalyst for Asymmetric Epoxidation of α,β-Enones[J]. Adv. Synth. Catal.2006,348:339-346. c) Li YW, Liu XY, Yang YQ, Zhao G.4-Substituted-α,α-diaryl-prolinols Improve the Enantioselective Catalytic Epoxidation of α,β-Enones[J]. J. Org. Chem.,2007,72:288-291.
[15]a) Marigo M, Johan F, Poulsen TB, Zhuang W, Jorgensen KA. Asymmetric Organocatalytic Epoxidation of α,β-Unsaturated Aldehydes with Hydrogen Peroxide[J]. J. Am. Chem. Soc.,2005, 127:6964-6965. b) Wang XW, List B. Asymmetric Counteranion-Directed Catalysis for the Epoxidation of Enals[J]. Angew. Chem. Int. Ed.,2007,47:1119-1122.
[16]Wang XW, Reisinger CM, List B. Catalytic Asymmetric Epoxidation of Cyclic Enones[J]. J. Am. Chem. Soc.,2008,130:6070-6071.
[17]Wu XY, She XG, Shi YA.Highly Enantioselective Epoxidation of α,β-Unsaturated Esters by Chiral Dioxirane[J].J. Am. Chem. Soc.,2002,124:8792-8793.
[18]a) Arai S, Shioiri T. Catalytic Asymmetric Darzens Condensation Under Phase-Transfer-Catalyzed Conditions[J]. Tetrahedron Lett.,1998,39:2145-2148. b) Bako P, Vizardi K, Bajorm Z, Toke L. Synthesis and Application in Asymmetric Synthesis of Azacrown Ethers Derived from D-Glucose[J]. Chem. Commun.1998,1193-1195. c) Bako P, Czinege E, Bako T, Czugler M, Toke L. Asymmetric C-C Bond Forming Reaction with Chiral Crown Catalysts Derived from D-Glucose and D-Galactose[J].Tetrahedron:Asymmetry 1999,10: 4539-4551
[19]Arai S, Shirai Y, Ishida T, Shioiri T. Phase-Transfer Catalyzed Asymmetric Darzens Reaction of Cyclic a-Chloro Ketones[J]. Chem. Commun.1999,49-50
[20]Arai S, Shioiri T. Asymmetric Darzens Reaction Utilizing Chloromethyl Phenyl Sulfone Under Phase-Transfer Catalyzed Conditions[J]. Tetrahedron 2002,58:1407-1413.
[21]a) Arai S, Tokumaru K, Aoyama T. Phase-Transfer Catalyzed Asymmetric Darzens Reaction Using a New Chiral Ammonium Salt[J]. Tetrahedron Lett.,2004,45:1845-1848.b) Achard TJR, Belokon YN, Ilyin M, Moskalenko M, North M, Pizzato F. Enantio-and Diastereoselective Darzens Condensations[J]. Tetrahedron Lett.,2007,48:2965-2969.
[22]Imashiro R, Yamanaka T, Seki M. Catalytic Asymmetric Synthesis of Glycidic Amides via Chiral Sulfur Ylides[J]. Tetrahedron:Asymmetry,1999,10:2845-2851.
[23]a) Aggarwal VK, Hynd G, Picoul W, Vasse, JL. Highly Enantioselective Darzens Reaction of a Camphor-Derived Sulfonium Amide to Give Glycidic Amides and Their Applications in Synthesis[J]. J. Am. Chem. Soc.,2002,124:9964-9965; b) Aggarwal VK, Charmant JPH, Fuentes D, Harvey JN, Hynd G, Ohara D, Picoul W, Smith C, Vasse J L, Winn C L. Highly Enantioselective Synthesis of Glycidic Amides Using Camphor-Derived Sulfonium Salts. Mechanism and Applications in Synthesis[J]. J. Am. Chem. Soc.2006,128:2105-2114.
[24]a) Guchi D, Sorimachi K, Terada M. Organocatalytic Asymmetric Direct Alkylation of a-Diazoester via C-H Bond Cleavage[J]. J. Am. Chem. Soc.2005,127:9360-9361. b) imoto T, Maruoka K.. Design of Chiral Dicarboxylic Acid for Asymmetric Mannich Reaction of Arylaldehyde N-Boc Imines and Diazo Compound[J]. J. Am. Chem. Soc.2007,129: 10054-10055.
[25]Hashimoto T, Uchiyama N, Maruoka KJ. Trans-Selective Asymmetric Aziridination of Diazoacetamides and N-Boc Imines Catalyzed by Axially Chiral Dicarboxylic Acid[J]. J. Am. Chem. Soc.2008,130:14380-14381.
[26]a) Yao WG, Wang JB. Direct Catalytic Asymmetric Aldol-Type Reaction of Aldehydes with Ethyl Diazoacetate[J]. Org. Lett.2003,5:1527-1530. b) Trost BM, Malhotra S, Fried BA. Magnesium-Catalyze Asymmetric Direct Aldol Addition of Ethyl Diazoacetate to Aromatic, Aliphatic, and α,β-Unsaturated Aldehydes[J]. J. Am. Chem. Soc.2009,131:1674-1675.
[27]a) Tony KMS, To L, Lee M, Chi ML. Asymmetric epoxidation of cis-alkenes with arabinose-derived ketones:enantioselective synthesis of the side chain of Taxol[J]. Tetrahedron 2006,62:6621-6629. b) Feske BD, Stewart JD. Chemoenzymatic formal total synthesis of (-)-bestatin[J]. Tetrahedron:Asymmetry 2005,16:3124-3127.
[28]a) Zhang Y, Desai A, Lu Z, Hu G, Ding Z, Wuff WD. Catalytic Asymmetric Aziridination with Borate Catalysts Derived from VANOL and VAPOL Ligands:Scope and Mechanistic Studies [J]. Chem. Eur. J.2008,14:3785-3803. b) Casarrubios L, Perez JA, Brookhart M, Templeton JL. Lewis Acid-Catalyzed Synthesis of Aziridines [J]. J. Org. Chem 1996,61:8358-8359.