一、氰醇和含氟仲醇的化学法动力学拆分研究；二、α，α-二氟-γ-丁内酯的合成新方法尝试
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摘要
仲醇的非酶动力学拆分是当前的研究热点。其中一些小分子催化剂具有较高的催化活性,如(R)-2,3-二氢-2-苯-咪唑[2,1-b]苯并噻唑[(R)-苯并四咪唑]。(R)-苯并四咪唑作为高效的非酶酰化转移催化剂,在催化一系列芳基烷基仲醇的拆分反应中,具有较高的催化活性及立体选择性。反应的立体选择性取决于底物结构中芳环与配体阳离子之间的π-π及Cation-π相互作用的强弱。本文将探索(R)-苯并四咪唑等小分子催化剂对氰醇和含氟仲醇等底物的拆分。
以卤代氮杂环和D-苯甘氨醇为起始原料通过两到三步反应合成得到一系列(R)-苯并四咪唑类催化剂(吡啶类、苯并噻唑类、异喹啉类)。
研究了(R)-苯并四咪唑类催化剂对氰醇类化合物的拆分。优化反应条件后,对扁桃腈的拆分反应对映性选择因子(s)值提高到7.66。推导出此类含简单л结构的芳基底物拆分反应中存在竞争性反应机理:氰基与催化剂阳离子之间形成的Cation-л相互作用导致过渡态Model 2;苯环与催化剂阳离子之间形成的Cation-л相互作用导致过渡态Model 1,两种过渡态同时存在导致s值降低及产物的构型与Birman报道的结果相反。(R)-苯并四咪唑类催化剂对一系列底物的拆分研究初步证实了上述竞争性反应机理。
研究了(R)-苯并四咪唑对2,2-二氟-3-羟基-3-芳基-丙酸酯的动力学拆分。研究表明当底物上含有苯环(或苯环上有供电子基团取代基)或萘环(延伸的苯环),拆分反应的s值等于或高于20。制各级的拆分实验研究为大量制备2,2-二氟-3-羟基-3-芳基-丙酸酯类化合物提供了一种新方法。
本文采用新型路线合成抗肿瘤药物Gemcitabine的重要中间体:α,α-二氟-γ-丁内酯。二氟碘乙酸乙酯含氟砌块和烯丙基苄醚发生自由基加成反应生成5-苄氧基-2,2-二氟-4-碘-戊酸乙酯,再经过消除反应、双羟化反应后分子内内酯化关环得到目标产物α,α-二氟-γ-丁内酯。
Recently, nonenzymatic kinetic resolution of racemic s econdary alcohols has been an active research topic. Small molecules of organocatalysts have been designed and synthesized for this purpose, some of which showed high efficiency. As an efficient nonenzymatic acyl transfer catalyst, (R)-2,3-dihydro-2-Phenyl-imidazo [2,1-b]benzothiazole [(R)-benzotetramisole] displayed high efficiency and selectivity for the kinetic resolution of a series ofα-alkyl benzylic alcohols. In the kinetic resolution catalyzed by (R)-benzotetramisole, the enantio-selectivity depended on how strong are theπ-πand the cation-πinteractions between the benzene ring of substrate and the aromatic system of the catalyst. In this thesis, we extended the application of organocatalyst to cyanohydrins and fluorinated secondary alcohols.
A series of catalysts derived from (R)-benzotetramisole were preparaed via two or three steps using heterocyclic compounds( pyridine, isoquinoline or benzothiazole) and (R)-phenylglycinol as starting material.
Kinetic resolution of mandelonitrile catalyzed by (R)-benzotetramisole was studied. The s value raised to 7.66 via the optimization of the reaction condition. A mechanism including two competitive interactions—cation-πinteractions between the benzene ring of substrate and the aromatic system of the catalyst(Model 1) or between the cyanic group of substrate and the aromatic system of the catalyst(Model 2)—was proposed to explain the low s value and the opposite configuration of the product relative to Birman's result. The mechanism was preliminary proved via the KR of a series of different substrates catalyzed by (R)-benzotetramisole.
The KR of a series of 2,2-difluoro-3-hydroxy-3-aryl-propionates with (R)-benzotetramisole as the catalyst was investigated. The result showed that when the aryl group in the substrate was a phenyl (or a phenyl substituted by an electron-donating group) or a naphthyl (an extended phenyl) group, the system could give an s value equal to or higher than 20. Preparative KR examples demonstrated the applicability of this method in the preparation of enantiomerically pure 2,2-difluoro-3 -hydroxy-3-aryl-propionates.
5-(Benzyloxymethyl)-3,3-difluoro-4-hydroxy-dihydrofuran-2(R)-one is the key intermediate for the synthesis of antitumor drug Gemcitabine and it's analogues. In this dissertation, A novel and practical route to the fluorinated lactone was developed. The radical addition of ethyl iododifluoroacetate with allyl benzyether followed by dehydroiodination and dihydroxylation gave the difluoromethylenated lactone.
以卤代氮杂环和D-苯甘氨醇为起始原料通过两到三步反应合成得到一系列(R)-苯并四咪唑类催化剂(吡啶类、苯并噻唑类、异喹啉类)。
研究了(R)-苯并四咪唑类催化剂对氰醇类化合物的拆分。优化反应条件后,对扁桃腈的拆分反应对映性选择因子(s)值提高到7.66。推导出此类含简单л结构的芳基底物拆分反应中存在竞争性反应机理:氰基与催化剂阳离子之间形成的Cation-л相互作用导致过渡态Model 2;苯环与催化剂阳离子之间形成的Cation-л相互作用导致过渡态Model 1,两种过渡态同时存在导致s值降低及产物的构型与Birman报道的结果相反。(R)-苯并四咪唑类催化剂对一系列底物的拆分研究初步证实了上述竞争性反应机理。
研究了(R)-苯并四咪唑对2,2-二氟-3-羟基-3-芳基-丙酸酯的动力学拆分。研究表明当底物上含有苯环(或苯环上有供电子基团取代基)或萘环(延伸的苯环),拆分反应的s值等于或高于20。制各级的拆分实验研究为大量制备2,2-二氟-3-羟基-3-芳基-丙酸酯类化合物提供了一种新方法。
本文采用新型路线合成抗肿瘤药物Gemcitabine的重要中间体:α,α-二氟-γ-丁内酯。二氟碘乙酸乙酯含氟砌块和烯丙基苄醚发生自由基加成反应生成5-苄氧基-2,2-二氟-4-碘-戊酸乙酯,再经过消除反应、双羟化反应后分子内内酯化关环得到目标产物α,α-二氟-γ-丁内酯。
Recently, nonenzymatic kinetic resolution of racemic s econdary alcohols has been an active research topic. Small molecules of organocatalysts have been designed and synthesized for this purpose, some of which showed high efficiency. As an efficient nonenzymatic acyl transfer catalyst, (R)-2,3-dihydro-2-Phenyl-imidazo [2,1-b]benzothiazole [(R)-benzotetramisole] displayed high efficiency and selectivity for the kinetic resolution of a series ofα-alkyl benzylic alcohols. In the kinetic resolution catalyzed by (R)-benzotetramisole, the enantio-selectivity depended on how strong are theπ-πand the cation-πinteractions between the benzene ring of substrate and the aromatic system of the catalyst. In this thesis, we extended the application of organocatalyst to cyanohydrins and fluorinated secondary alcohols.
A series of catalysts derived from (R)-benzotetramisole were preparaed via two or three steps using heterocyclic compounds( pyridine, isoquinoline or benzothiazole) and (R)-phenylglycinol as starting material.
Kinetic resolution of mandelonitrile catalyzed by (R)-benzotetramisole was studied. The s value raised to 7.66 via the optimization of the reaction condition. A mechanism including two competitive interactions—cation-πinteractions between the benzene ring of substrate and the aromatic system of the catalyst(Model 1) or between the cyanic group of substrate and the aromatic system of the catalyst(Model 2)—was proposed to explain the low s value and the opposite configuration of the product relative to Birman's result. The mechanism was preliminary proved via the KR of a series of different substrates catalyzed by (R)-benzotetramisole.
The KR of a series of 2,2-difluoro-3-hydroxy-3-aryl-propionates with (R)-benzotetramisole as the catalyst was investigated. The result showed that when the aryl group in the substrate was a phenyl (or a phenyl substituted by an electron-donating group) or a naphthyl (an extended phenyl) group, the system could give an s value equal to or higher than 20. Preparative KR examples demonstrated the applicability of this method in the preparation of enantiomerically pure 2,2-difluoro-3 -hydroxy-3-aryl-propionates.
5-(Benzyloxymethyl)-3,3-difluoro-4-hydroxy-dihydrofuran-2(R)-one is the key intermediate for the synthesis of antitumor drug Gemcitabine and it's analogues. In this dissertation, A novel and practical route to the fluorinated lactone was developed. The radical addition of ethyl iododifluoroacetate with allyl benzyether followed by dehydroiodination and dihydroxylation gave the difluoromethylenated lactone.
引文
1 王丹,李亚,何浪,手性药物及其开发利用,现代医药卫生,2007,23(6),837-838.
2马红敏,邵瑞链,马治华,成俊然,动力学拆分法研究进展,有机化学,2000,20(4),454-463.
3 Victor,B.,Martin,S.,Sharpless,K.B.,Kinetic resolution of racemic allylic alcohols by enantioselective epoxidation.A route to substances of absolute enantiomeric purity? J.Am.Chem.Soc.,1981,103(20),6237-6240.
4 Vedejs,E.,Jure,M.,Efficiency in nonenzymatic kinetic resolution,Angew.Chem.Int.Ed.,2005,44(26),3974-4001.
5 Dalko,P.I.,Moisan,L.,In the gloden age of organocatalysis,Angew.Chem.Int.Ed,2004,43(39),5138-5175.
6 Vedejs,E.O.,Daugulis.O.,Diver,S.T.,Enantioselective acylations catalyzed by chiral phosphines,J.Org.Chem.,1996,61(2),430-431.
7 Vedejs.E.,Daugulis.O.,Tuttle.N.,Desymmetrization of meso-hydrobenzoin using chiral,nucleophilic phosphine Catalysts,J.Org.Chem.,2004,69(4),1389-1392.
8 Vedejs.E.,Daugulis.O.,2-Aryl-4,4,8-trimethyl-2-phosphabicyclo[3.3.0]octanes:reactive chiral phosphine catalysts for enantioselective acylation,J.Am.Chem.Soc.,1999,121(24),5813-5814.
9 Vedejs,E.,Dauglis.A.,Comparison of monocyclic and bicyclic phospholanes as acyl-transfer catalysts,J.Org.Chem.,2003,68(13),5020-5027.
10 Vedejs,E.,Daugulis,O.,A highly enantioselective phosphabicyclooctane catalyst for the kinetic resolution of benzylic alcohols,J.Am.Chem.Soc.,2003,125(14),4166-4173.
11 Vedejs,E.,Mackay,J.A.;Kinetic resolution of allylic alcohols using a chiral phosphine catalyst, Org. Lett., 2001,5(4), 535-536.
12 Jarvo, E.R., Copeland, G T., Papaioannou, N., Bonitatebus, P. J., Miller, S. J., Abiomimetic approach to asymmetric acyl transfer catalysis, J. Am. Chem. Soc.,1999, 121(50), 11638-11634.
13 Vasbinder, M. M., Jarvo, E. R., Miller, S. J., Incorporation of peptide isosteres into enantioselective peptide-based catalysts as mechanistic probes, Angew. Chem.Int. Ed, 2001, 40(15), 2824-2827.
14 Fierman, M. B., O'Leary, D. J., Steinmetz, W. E., Miller, S. J., Structure-selectivity relationships and structure for a peptide-based enantioselective acylation catalyst, J. Am. Chem. Soc, 2004,126(22), 6967-6971.
15 Copeland, G. T., Jarvo, E. R., Miller, S. J., Minimal acylase-like peptides.conformational control of absolute stereospecificity, J. Org. Chem., 1998, 63(20),6784-6785.
16 Copeland, G. T., Miller, S. J., Selection of enantioselective acyl transfer catalysts from a pooled peptide library through a fluorescence-based activity assay: an approach to kinetic resolution of secondary alcohols of broad structural scope, J.Am. Chem. Soc, 2001, 123(27), 6494-6502.
17 Jarvo, E. R., Evans, C. A., Copeland, G. T., Miller, S. J., Fluorescence-based screening of asymmetric acylation catalysts through parallel enantiomer analysis.Identification of a catalyst for tertiary alcohol resolution, J. Org. Chem., 2001,66(16), 5522-5527.
18 Copeland, G. T., Miller, S. J., A chemosensor-based approach to catalyst discovery in solution and on solid support, J. Am. Chem. Soc, 1999, 727(17),4306-4307.
19 Terakado, D., Koutaka, H., Oriyama, T. Organocatalytic kinetic resolution of racemic primary alcohols using a chiral 1,2-diamine derived from (S)-proline,Tetrahedron: Asymmetry, 2005,16(6), 1157-1165,.
20 Oriyama, T., Hori, Y., Imai, K., Sasaki, R., Nonenzymic enantioselective acylation of racemic secondary alcohols catalyzed by a SnX2-chiral diamine complex, Tetrahedron Lett, 1996, 57(47), 8543-8546.
21 Sano, T., Imai, K., Ohashi, K., Oriyama, T., Catalytic asymmetric acylation of racemic secondary alcohols with benzoyl chloride in the presence of a chiral diamine, Chem. Lett, 1999, (3), 265-266.
22 Vedejs, E., Chen, X., Kinetic resolution of secondary alcohols. Enantioselective acylation mediated by a chiral (dimethylamino)pyridine derivative, J. Am. Chem.Soc, 1996,118(7), 1809-1810.
23 Vedejs, E., Chen, X., Parallel kinetic resolution, J. Am. Chem. Soc, 1997,119(10), 2584-2585.
24 Ruble, J. C, Tweddell, J., Fu, G. C, Kinetic resolution of arylalkylcarbinols catalyzed by a planar-chiral derivative of DMAP: A new benchmark for nonenzymic acylation, J. Org. Chem., 1998, 63(9), 2794-2795.
25 Ruble, J. C, Latham, H. A., Fu, G. C., Effective kinetic resolution of secondary alcohols with a planar-chiral analog of 4-(dimethylamino)pyridine. Use of the Fe(C_5Ph_5) group in asymmetric catalysis, J. Am. Chem. Soc, 1997, 119(6),1492-1493.
26 Fu, G. C., Asymmetric catalysis with "planar-chiral" derivatives of 4-(dimethyl-amino)pyridine,Acc. Chem. Res., 2004, 57(8), 542-547.
27 Spivey, A. C., Arseniyadis, S., Fekner, T., Maddafordb, A., Leeseb, D. P., Rapid,room-temperature acylative kinetic resolution of sec-alcohols using atropisomeric 4-aminopyridine/triphenylphosphine catalysis, Tetrahedron, 2006,62(2-3), 295-301.
28 Spivey, A. C., Leese, D. P., Zhu, F., et.al, New atropisomericbiaryl derivatives of 4-aminopyridine identification of an improved nucleophilic catalyst for asymmetric acylation of sec-alcohols, Tetrahedron, 2004, 60(20), 4513-4525.
29 Spivey, A. C., Fekner, T., Spey, S. E., Axially chiral analogues of 4-(dimethylamino)pyridine: novel catalysts for nonenzymatic enantioselective acylations,J.Org.Chem.,2000,65(10),3154-3159.
30 Spivey,A.C.,Fekner,T.,Spey,S.E.,Adams,H.,Configurationally stable biaryl analogues of 4-(dimethylamino)pyridine:A novel class of chiral nucleophilic catalysts,J.Org.Chem.,1999,64(26),9430-9443.
31 Kawabata,T.,Nagato,M.,Takasu,K.,Fuji,K.,Nonenzymic kinetic resolution of racemic alcohols through an "Induced Fit" process,J.Am.Chem.Soc.,1997,119(13),3169-3170.
32 Kawabata,T.,Yamamoto,K.,Momose,Y.,Yoshida,H.,Nagaoka,Y.,Fuji,K.,Kinetic resolution of amino alcohol derivatives with a chiral nucleophilic catalyst:access to enantiopure cyclic cis-amino alcohols,Chem.Commun.,2001,(24),2700-2701.
33 Birman,V.B.,Li,X.,Benzotetramisole:A remarkably enantioselective acyl transfer catalyst,Org.Lett.,2006,8(7),1351-1354.
34 Birman,V.B.,Li,X.,Jiang,H.,Uffman,E.W.,Influence of electronic and steric factors on 2,3-dihydroimidazo[1,2-a]pyridine-based enantioselective acylation catalysts,Tetrahedron,2006,62(2-3),285-294.
35 Birman,V.B.,Uffman,E.W.,Jiang,H.,Li,X.,Kibane,C.J.,2,3-Dihydro imidazo[1,2-a]pyridines:A new class of enantioselective acyl transfer catalysts and their use in kinetic resolution of alcohols,J.Am.Chem.Soc.,2004,126(39),12226 -12227.
36 Birman,V.B.,Guo,L.,Kinetic resolution of propargylic alcohols catalyzed by benzotetramisole,Org.Lett.,2006,8(21),4859-4861.
37 Birman,V.B.,Jiang,H.,Kinetic resolution of alcohols using a 1,2-dihydroimidazo[1,2-a]quinoline enantioselective acylation catalyst,Org.Lett.,2005,7(16),3445-3447.
38 Birman,V.B.,Li,X.,Homobenzotetramisole:an effective catalyst for kinetic resolution of aryl-cycloalkanols,Org.Lett.,2008,10(6),1115-1118.
39 Birman,V.B.,Jiang,H.,Li,X.M.,et.al,Kinetic resolution of 2-oxazolidinones via catalytic,enantioselective N-acylation,J.Am.Chem.Soc.,2006,128(20),6536-6537.
40 Yamada,S.,Misono,T.,Iwai,Y.,Masumizu,A.,Akiyama,Y.,New class of pyridine catalyst having a conformation switch system:asymmetric acylation of various sec-alcohols,J.Org.Chem.,2006,71(18),6872-6880.
41 Tao,B.,Ruble,C.,Hoic,D.A.,Nonenzymatic kinetic resolution of propargylic alcohols by a planar-chiral DMAP derivative:crystallographic characterization of the acylated catalyst,J.Am.Chem.Soc.,1999,121(21),5091-5092.
42 Priem,G.,Pelotier,B.,Macdonald,S.J.F.,et,al,The design of novel N-4'-pyridinyl-α-methyl proline derivatives as potent catalysts for the kinetic resolution of alcohols,J.Org.Chem.,2003,68(10),3844-3848.
43 Jones,G.B.,Shielding in organic synthesis,Tetrahedron,2001,57(38),7999-8016.
44 Meyer,E.A.,Castellano,R.K.,Diederich,F.,Interactions with aromatic rings in chemical and biological recognition,Angew.Chem.Int.Ed,2003,42(11),1210-1250.
45 Tsuzuki,S.,Mikami,M.,Yamada,S.,Origin of attraction,magnitude,and directionality of interactions in benzene complexes with pyridinium cations,J.Am.Chem.Soc.,2007,129(27),8656-8662.
46 Ma,J.M.,Dougherty,D.A.,The cation-л interaction,Chem.Rev.,1997,97(5),1303-1324
47 Gallivan,J.P.,Dougherty,D.A.,Cation-л interactions in structural biology,Proc.Natl.Acad.Sci.USA.,1999,96(17),9459-9464.
48 Minoux,H.,Chipot,C.,Cation-л interactions in proteins:can simple models provide an accurate description? J.Am.Chem.Soc.,1999,121(44),10366-10372.
49 Burley,S.K.,Petsko,G.A.,Amino-aromatic interactions in proteins,FEBS Lett,1986,203(2).139-143.
50 Verdonk,M.L.,Boks,G.J.,Kooijman,H.J.,Stereochemistry of charged nitrogen-aromatic interactions and its involvement in ligand-receptor binding,J.Comput.Aided.Mol.Des.,1993,7(2),173-182.
51 Sussman,J.L.,Harel,M.,Frolow,F.,Atomic structure of acetylcholinesterase from Torpedo califomica:a prototypic acetylcholine-binding protein,Science,1991,253(5022),872-879.
52 Cooper,C.E.,Jan,Y.L.,Ion channel genes and human neurological disease:recent progress,prospects,and challenges,Proc.Natl.Acad.Sci.USA.,1991,96(9),4759-4766.
53 Mccurdy,A.,Jimenez,L.,Stauffer,D.,Dougherty,D.,Biomimetic catalysis of S_N2 reactions through cation-л interactions.The role of polarizability in catalysis,J.Am.Chem.Soc.,1992,114(26),10314-10321.
54 Favre,I.,Moezydlowski,E.,Schild,L.,Biomimetic catalysis of S_N2 reactions through cation-л interactions.The role of polarizability in catalysis,J.Gen.Physiol.,1995,106(26),10314-10321.
55 Bradley,M.,Bucheler,U.S.,Walsh,C.T.,Redox enzyme engineering:conversion of human glutathione reductase into a trypanothione reductase.Biochemistry,1991,30(25),6124-6127.
56 Walther.H.,The sensitizing action of hematoporphyrin,Biochemische Zeitschrift,1911,30,276-317.
57 Henderson,G.B.,Murgolo,N,J.,Engineering the substrate specificity of glutathione reductase toward that of trypanothione reduction,Proc.Natl.Acad.Sci.USA.,1991,88(19),8769-8773.
58 Adak,S.,Mazumder,A.,Bancrjee,R.K.,Probing the active site residues in aromatic donor oxidation in horseradish peroxidase:involvement of an arginine and a tyrosine residue in aromatic donor binding,Biochem.J.,1996,314(3),985-991.
59 Lakshminarasimhan,P.,Sunoj,R.B.,Chandrasekhar,J.,Ramamurthy,V. Cation-л interaction controlled selective geometric photoisomerization of diphenylcyclopropane,J.Am.Chem.Soc.,2000,122(19),4815-4816.
60 Mccurdy,A.,Jimenez,L.,Stauffer,D.,Dougherty,D.,Biomimetic catalysis of S_N2 reactions through cation-л interactions.The role of polarizability in catalysis,J.Am.Chem.Soc.,1992,114(26),10314-10321.
61 Yamada,S.,Saitoh,M.,Misono,T.,Stereoselective synthesis of 1,2- and 1,4-dihydropyridines by using cation-л interaction as a conformation-controlling tool,Tetrahedron Lett,2002,43(33),5853-5857.
62 Yamada,S.,Morita,C.,Face-selective addition to a cation-л complex of a pyridinium salt:synthesis of chiral 1,4-dihydropyridines,J.Am.Chem.Soc.,2002,124(28),8184-8185.
63 Yamada,S.,Uematsu,N.,Yamashita,K.,Role of cation-л interactions in the photodimerization of trans-4-Styrylpyridines,J.Am.Chem.Soc.,2007,129(40),12100-12101.
64 Yamada,S.,Yamamoto,J.,Ohta,E.,Enantioselective cyclopropanation reaction using a conformationally fixed pyridinium ylide through a cation-л interaction,Tetrahedron Lett,2007,48(5),855-858.
65 Lei,Y.,Jeffrey,A.,Cation-л control of regiochemistry of intramolecular schmidt reactions en route to bridged bicyclic lactams,J.Am.Chem.Soc.,2007,129(10),2766-2767.
66 Katz,C.E.,Ribelin T.,Withrow,D.,et.al,Nonbonded,attractive cation-лinteractions in azide-mediated asymmetric ring expansion reactions,J Org.Chem.,2008,73(9),3318-3327.
67 Huang,T.B.,Wang,K.,Liu,L.F.,He,F.H.,Insertion of((di-iso-propyl)amino)(chloro)phosphenium cation into phenylcyclopropane ring:stereochemistry,regioselectivity and mechanism,Main Group Chemistry,1999,3(1),5-14.
68 Kaanumalle,L.S.,Sivaguru,J.,Arunkumar,N.,et.al,Cation-л interactions as a tool to enhance the power of a chiral auxiliary during asymmetric photoreactions within zeolites,Chem.Cummun.,2003,(1),116-117.
69 Natarajan,A.,Ramamurthy,V.,Asymmetric induction during photocyclization of chiral and achiral α -oxoamides within achiral zeolites,Org.Biomol.Chem.,2006,4(24),4533-4542.
70 Bremer,O.,Synthesis of nitrated 2,3-dihydropyrimidazoles,annalen,1936,521,286-297.
71 Copp,F.C.,Timmis,G.M.,Potential tumor inhibitors.Esters of 4-di(2-hydroxy -ethyl)aminopyridine and quaternary derivatives of 2,3-dihydroglyoxalino [1,2-a]pyridine,J..Chem.Soc.,1955,2021-2027.
72 Weiner,N.,Kaye,I.,N-2-Pyridylalkanolamines and esters,J.Org.Chem.,1949,14(5),868-872.
73 Gomtsyan,A.,Bayburt,E.K.,Schmidt,R.G.,et.al.Novel transient receptor potential vanilloid 1 receptor antagonists for the treatment of pain:Structureactivity relationships for ureas with quinoline,isoquinoline,quinazoline,phthalazine,quinoxaline,and cinnoline moieties,J..Med Chem,2005,48(3),744-752.
74 李再峰,罗富英,N-芳基-N'-取代噻唑基脲的合成与结构表征,化学研究与应用,2001,13(1),80-82.
75 Gregory,R.J.H.,Cyanohydrins in nature and the laboratory:biology,preparations,and synthetic applications,Chem.Rev.,1999,99(12),3649-3682.
76 Effenberger,F.,Synthesis and reactions of optically active cyanohydrins.Angewandte Chemie,1994,106(15/16),1609-1619.
77 Michael,N.,Catalytic asymmetric cyanohydrin synthesis,SynLett,1993,(11),807-820.
78 Herranz,R.,Castro-Pichel,J.,and Garcia-Lopez,T.,Tributyltin cyanide,a novel reagent for the stereoselective preparation of 3-amino-2-hydroxy acids via cyanohydrin intermediates,Synthesis,1989,(9),703-6.
79 Garcia,M.M.C.,Ruano,J.L.G.,Highly stereoselective hydrocyanation of optically pure α-sulfinyl aldehydes,Tetrahedron:Asymmetry,1998,9(5),859-864.
80 Terashima,S.,Synthesis of optically active and biologically active compounds,Synlett,1992,(9),691-702.
81 Golinski,M.,Brock,C.P.,Watt,D.,S.,Addition of tert-butyldimethyl- or tert-butyldiphenylsilyl cyanide to hindered ketones,J.Org.Chem.,1993,58(1),159-164.
82 Effenberger,F.,Gutterer,B.,Ziegler,T.,Enzyme-catalyzed reactions.7.Enantioselective esterification of racemic cyanohydrins and enantioselective hydrolysis or transesterification of cyanohydrin esters by lipases,Liebigs.Ann.Chem,1991,(1),47-54.
83 Hsu,S.H.,Wu,S.H.,Wang,Y.F.,Wong,C.H.,Lipase-catalyzed irreversible transesterification using enol esters:XAD-8 immobilized lipoprotein lipasecatalyzed resolution of secondary alcohols,Tetrahedron Lett.,1990,31(44),6403 -6406.
84 Inagaki,M.,Hiratake,J.,Nishioka T.,Oda,J.,Lipase-catalyzed kinetic resolution with in situ racemization:one-pot synthesis of optically active cyanohydrin acetates from aldehydes,J.Am.Chem.Soc.,1991,113(24),9360-9361.
85 Inagaki,M.,Hiratake,J.,Nishioka,T.,Oda,J.,One-pot synthesis of optically active cyanohydrin acetates from aldehydes via lipase-catalyzed kinetic resolution coupled with in situ formation and racemization of cyanohydrins,J..Org.Chem.,1992,57(21),5643-5649.
86 Ohta,H.,Miyamae,Y.,Tsucchihashi,G.,Asymmetric hydrolysis of aryloxyacetaldehyde cyanohydrin acetates,Argric.Biol.Chem.,1986,50(12),3181-3184.
87陈沛然,手性氰醇化合物的生物催化合成及其应用于生物活性分子合成中的研究,中国科学院上海有机化学研究所博士论文,2003,133-208.
88 Date,J.,Dull,D.,Mosher,H.,α-Methoxy-α-trifluoromethylphenylacetic acid,a versatile reagent for the determination of enantiomeric composition of alcohols and amines,J.Org.Chem.,1969,34(9),2543-2549.
89 Mendez,E.,Brieva,R.,Rebolledo,F.,Gotor,V.,Optically active(S)-ketone- and (R)-aldehyde-cyanohydfins via an(R)-oxynitrilase-catalyzed transcyanation.Chemoenzymic syntheses of 2-cyanotetrahydrofuran and 2-cyanotetra -hydropyran,J.Chem.Soc.,Chem.Commun.,1995,(10),989-990.
90 Effenberger,F.,Ziegler,T.,Forster,S.,Enzyme-catalyzed cyanohydrin preparation in organic solvents,Angewandte Chemie,1987,99(5),491-492.
91 Brussee,J.,Roos,E.C.,van der Gen,A.,Bioorganic synthesis of optically active cyanohyddns and acyloins,Tetrahedron Lett.,1988,29(35),4485-4488.
92 Brussee,J.,Loos,W.T.,Kruse,C.G.,van der Gen,A.Synthesis of optically active silyl protected cyanohydrins,Tetrahedron,1990,46(3),979-986.
93 Gerrits,P.J.,Zumbragel,F.,Marcus,J.,Analyzing the hydrocyanation reaction:chiral HPLC and the synthesis of racemic cyanohydrins,Tetrahedron,2001,57(41),8691-8698.
94 Belokon,Y.N.,Blacker,A.J.,Carta,P.,et.al,Synthetic and mechanistic studies on asymmetric cyanohydrins synthesis using a titanium(salen) bimetallic catalyst,Tetrahedron,2000,60(46),10433-10447.
95 Gokel,G.W.,Wall,S.L.D.,Meadow,E.S.,Experimental evidence for alkali metal cation-л interactions,Eur.J.Org.Chem.,2000,(17),2967-2978.
96 Tsuzuki,S.,Mikami,M.,Yamada S.,Origin of attraction,magnitude,and directionality of interactions in benzene complexes with pyridinium cations,J.Am.Chem.Soc.,2007,129(27),8656-8662.
97 Yamada,S.,Misono,T.,Tsuzuki,S.Cation-л interactions of a thiocarbonyl group and a carbonyl group with a pyridinium nucleus,J.Am.Chem.Soc,2004,126(31),9862-9872.
98 卿凤翎,高文忠,钯催化下(Z)-3-碘-3-三氟甲基-1-芳基烯丙醇与末端炔烃的 偶联反应,有机化学,2000,20(5),764-765.
99 Cristiane,P.,Mariada Grace,N.,Effects of organic solvents and ionic liquids on the aminolysis of(RS)-methyl mandelate catalyzed by lipases,Tetrahedron:Asymmetry,2006,17(3),428-433.
100 Zhao,H.T.,Qin,B.,Liu,X.H.,Feng,X.M.,Enantioselective trifluoromethylation of aromatic aldehydes catalyzed by combinatorial catalysts,Tetrahedron,2007,63(29),6822-6826.
101 Steele,R.M.,Monti,C.,Gennari,C.,et.al,Enantioselective cyanosilylation of aldehydes catalysed by a diastereomedc mixture of atropisomedc thioureas,Tetrahedron:Asymmetry,2006,17(6),999-1006.
102 Schmidt,M.,Herve',S.,Klempier,N.,Griengl,H.,Preparation of optically active cyanohydrins using the(S)-hydroxynitrile lyase from Hevea brasiliensis,Tetrahedron,1996,52(23),7833-7840.
103 Iseki,K.,Catalytic asymmetric synthesis of chiral fluoroorganic compounds,Tetrahedron,1998,54(46),13887-13914.
104 卿凤翎,邱小龙,“有机氟化学'2007,科学出版社,北京,317-349.
105 Ma,J.,Cahard,D.,Asymmetric fluorination,trifluoromethylation,and perfluoroalkylation reactions,Chem.Rev.,2004,104(12),6119-6146.
106 Gelb,M.H.,Fluoro ketone phospholipid analogs:new inhibitors of phospholipase A2,J.Am.Chem.Soc.,1986,108(11),3146-3147.
107 Jimenez,O.,Bosch,M.P.,Guerrero,A.,Practical and efficient synthesis of alkyl,alkenyl and aryl-alkyl α,α-difluoro esters as precursors of potential inhibitors of the pheromone catabolism in insects,Synthesis,2000,(13),1917-1924.
108 彭荣达,郝健,含氟β-氨基酸及其衍生物的合成进展,有机化学,2005,25(5),485-495.
109 Fokina,N.A.,Kornilov,A.M.,Kukhar,V.P.,The Mitsunobu reaction in the synthesis of α,α-difluoro-β-amino acids,J.Fluorine.Chem.,2001,111(1),69-76.
110 Kuroki,Y.,Asada,D.,Iseki,K.,Enantioselective synthesis of 2,2-difluoro 3-hydroxy carboxylates by rhodium-catalyzed hydrogenation,Tetrahedron Lett.,2000,41(50),9853-9858.
111 Kloetzing,R.J.,Thaler,T.,Knochel,P.,An improved asymmetric reformatsky reaction mediated by(-)-N,N-dimethylaminoisoborneol,Org.Lett.,2006,8(6),1125-1128.
112 Andre,J.M.,Martinez,M.A.,Pedrosa,R.,Perez-Encabo,A.Synthesis of chiral α,α-difluoro β-hydroxy esters by enantioselective Reformatskii reaction,Synthesis,1996,(9),1070-1072.
113 Iseki,K.,Kuroki,Y.,Asada,D.,Kobayashi,Y.Isolation of α,α-difluoroketene silyl acetal and its application to asymmetric aldol reactions,Tetrahedron Lett.,1997,.38(8),1447-1448.
114 Iseki,K.,Kuroki,Y.,Asada,D.,Takahashi,M.,Kishimoto,S.,Kobayashi,Y.,Asymmetric aldol addition of aldehydes to a difluoroketene silyl acetal catalyzed by chiral Lewis acids,Tetrahedron,1997,53(30),10271-10280.
115 Linderman,R.J.,Graves,D.M.,Oxidation of fluoroalkyl-substituted carbinols by the Dess-Martin reagent,J.Org.Chem.,1989,54(3),661-668.
116 Fukuda,H.,Kitazume,T.A.,General route to N'-(2,2-difluoro-3-hydroxy alkanoyl)nornicotines,J.Fluorine.Chem,1995,74(2),171-176.
117 Meadows,E.S.,Wall,S.L.D.,Barbour,L,J.,Gokel,G.W.,Alkali metal Cation-π interaction observed by using a lariat ether model system,J.Am.Chem.Soc.,2001,123(13),3092-3107.
118 Ngola,S.M.,Dougherty,D.A.,Concerning the effects of aromatic ring fluorination on the Cation-π interaction and other molecular recognition phenomena in aqueous media,J.Org.Chem.,1998,63(14),4566-4567.
119 黄贤海,施国强,有机分子中引入二氟亚甲基的最新进展,有机化学,1997,17(5),394-410.
120 Berkiwitz,D.B.,Sloss,D.G.,Diallyl(lithiodifluoromethyl)phosphonate:A new reagent for the introduction of the(difluoromethylene)phosphonate functionality,J.Org.Chem.,1995,60(21),7047-7050.
121 Matulic-Adamic,J.,Haeberli,P.,Usman,N.,Synthesis of 5'-deoxy-5'-difluoromethyl phosphonate nucleotide analogs,J.Org.Chem.,1995,60(8),2563-2569.
122 Schirlin,D.,Baltzer,S.,Altenburger,J.A.,Tarnus,C.,Remy,J.M.,Difluoromethylene-ketone retroamide,a versatile concept of inactivation of proteolytic enzymes,Tetrahedron,1996,52(1),305-318.
123 吴繁花,含氟γ-内酯的合成研究,华东理工大学博士论文,2005.
124 Watanabe,K.A.,Reichman,U.,Hirota,K.,Lopez,C.,Fox,J.J.,Nucleosides.synthesis and antiherpes virus activity of some 2'-fluoro-2'-deoxyarabino furanosyl pyrimidine nucleosides,J.Med.Chem,1979,22(1),21-24.
125 Etzold,G.,Hintsche,R.,Kowollik,G.,Langen,P.,Nucleosides of fluoro sugars.Ⅵ.Synthesis and reactivity of 3'-fluoro-and 3'-chloro-3'-deoxythymidine,Tetrahedron,1971,2 7(12),2463-2472.
126 Balzarini,J.,Baba,M.,Pauwells,R.,Herdewijn,P.,De Clercq,E.,Anti-retrovirus activity of 3'-fluoro- and 3'-azido-substituted pyrimidine 2',3'-dideoxynucleoside analogs,Biochem.Pharmacol,1988,37(14),2847-2856.
127 Hertel,L.W.,Kroin,J.S.,Misner,J.W.,Tustin,J.M.,Synthesis of 2-deoxy-2,2-difluoro-D-ribose and 2-deoxy-2,2'-difluoro-D-ribofuranosyl nucleosides,J.Org.Chem,1988,53(11),2406-2409.
128 Toshiyuki,I.,Kazutoshi,K.,Kazuhisa,Y.,et.al,Synthesis and biological activity of point-fluorinated pheromone analogues of Eldana saccharina,Eur.J.Org.Chem.,2004,(2),406-412.
129 Toshiyuki,T.,Kohei,S.,Kazutoshi,K.,Asymmetric synthesis of both enantiomers of α,α-difluoroeldanolide an interesting property of their biological activity,Tetrahedron Lett.,1998,39(23),4071-4047.
130 Pankiewicz,K.W.,Fluorinated nucleosides,Carbohydr.Res,2000,327(1-2), 87-105.
131 Fuchigami,T.,Fujita,T.,Electrolytic partial fluorination of organic compounds.14.The first electrosynthesis of hypervalent iodobenzene difluoride derivatives and its application to indirect anodic gem-difluorination,J.Org.Chem.,1994,59(24),7190.
132 Ogura,K.,Ogu,K.,Ayabe,T.,et.al,Stereoselective formation of a-fluoro-a-trifluoromethyl-g-lactones starting from γ-hydroxy-α,β-unsaturated sulfones and a hexafluoropropene-diethylamine adduct(PPDA),Tetrahedron Lett,1997,38(29),5173-5176.
133 Okada,M.,Nakamura,Y.,Horikawa,H.,et.al,Fluoro-lactonization of 4-alkenoic acid derivatives with N-fluoropentachloropyridinium triflate,J.Fluorine.Chem,1997,82(2),157-161.
134 Sawaguchi,M.,Hara,S.,Fukuhara,T.,Yoneda,N.,Fluorocyclization of unsaturated alcohols and carboxylic acids by iodotoluene difluoride and amine-HF complexes,J.Fluorine.Chem,2000,104(2),277-280.
135 Ramachandran,P.V.,Padiya,K.J.,Rauniyar,V.,Reddy,M.V.R.,Brown,H.C.,Asymmetric synthesis of γ-perfluoroalkyl(aryl)butyrolactones via organoboranes,Tetrahedron Letters,2004,45(5),1015-1017.
136 Naddaka,V.,Klopfer,E.,Saeed,S.,et.al,Process for preparing gemcitabine and associated intermediates,W.O Pat 2007070804 A2,2007.
137 Kim,M.S.,Kim,Y.J.,Choi,J.H.,et.al,A manufacturing process of 2',2'-difluronucleoside and intermediate,W.O Pat 2007069838 A1,2007.
138 Palle,V.,Raghavendra,A.,Nariyam,S.M.,et.al,Preparation of gemcitabine,W.O Pat 2007117760 A2,2007.
139 Kotra,L.P.,Xiang,Y.J.,Newton,M.G.,Schinazi,R.F.,et.al,Structureactivity relationships of 2'-deoxy-2',2'-difluoro-1-erythro-pentofuranosyl Nucleosides,J.Med.Chem,1997,40(22),3635-3644.
140 Bravo,P.,Frigerio,M.,Melloni,A.,et.al,Stereoselective synthesis of both enantiomers of trifluoro-valcrolactone and Pentafluro-caprolactone,Eur.J.Org.Chem.,2002,(12):1895-1902.
141 Ge,P.,Kirk,K.L.,Synthesis of 2-deoxy-2-halo-L-ascorbic acids,J.Org.Chem.,1997,62(10),3340-3343.
142 Xiao,F.H.,Wu,F.H.,Shen,Y.J.,Zhou,L.F.,Synthesis of α,α-difluoro-γ-butyrolactones via ethyl iododifluoroacetate,J.Fluorine.Chem,2005,126(1),63-67.
143 李纪国,孙曙光,张正,相转移催化法制苄醚,化学试剂,1986,8(6),370-371.
144 Zhao,G.,Sun,H.L.,Cp_2TiCl_2(cat)/Zn system promoted addition reaction of bromo-difluoro acetate with the election-deficient gem-dicyanoalkenes,J.Fluorine.Chem,2001,111(2),217-219.
145 Yang,Z.Y.,Burton,D.J.,A novel and practical method for the preparation of α,α-difluorofunctionalized esters,J.Chem.Soc,Chem.Commun.,1992,(3)233-234.
146 Yang,Z.Y.,Burton,D.J.,Nickel-catalyzed reaction of iododifluoroacetates with alkenes and zinc:A novel and practical route to α,α-difluoro-functionalized esters and α,α,ω,ω-tetrafluoro diesters,J.Org.Chem.,1992,57(19),5144-5149.
147 Yang,Z.,Burton,D.,A new approach to α,α-difluoro-functionalized esters,J.Org.Chem.,1991,56(17),5125-5132.
148 Murakami,S.,Ishii,H.,Fuchigami,T.,Eletrosynthesis of ethyl α,α-difluoro-α-(phenylseleno)acetate and its photochemical synthetic application,J.Fluorine Chem,2004,125(4),609-614.
149 Sato,K.,Omote,M.,Ando,A.,Kumadaki,A.I.,Reaction of ethyl bromodifluoroacetate in the presence of copper powder,J.Fluorine.Chem.,2004,125(4),509-515.
150 Schwaebe,M.K.,Mccarthy,J.R.,Whitten,J.P.,Nickel(0)-catalyzed coupling of vinylzirconiums to α-bromo-α,α-difluoro esters.Convenient generation of a functionalized allyldifluoro moiety,Tetrahedron Lett.,2001,41(6),791-794.
151 余审义,陈馥衡,Ando催化剂的发现、研究及催化机理,化学试剂,1999,21,(5),290-293.
152 Yadav,V.K.,Kapoor,K.K.,KF Adsorbed on alumina effectively promotes the epoxidation of electron deficient alkenes by anhydrous t-BuOOH,Tetrahedron,1996,52(10),3659-3668.
153 Alloum,B.A.,Villemin,D.,Potassium fluoride on alumina:an easy preparation of diazo carbonyl compounds,Synth.Commun,1989,19(13-14),2567-2671.
154 Kabalka,G.W.,Wang,L.,Namboodiri,V.,Pagni,R.M.,Rapid microwave-enhanced,solventless Sonogashira coupling reaction on alumina,Tetrahedron Lett,2000,41(27),5151-5154.
155 Kabalka,G.W.,Pagni,R.M.,Hair,C.M.,Solventless suzuki coupling reactions on palladium-doped KF/Al_2O_3,Org.Lett.,1999,1(9),1423-1425.
156 Nakano,Y.,Shi,W.,Nishii,Y.,Igarashi,M.J.,Knoevenagel reaction of malononitrile with methyl ketones followed by double cyclization catalyzed by potassium fluoride-coated alumina,Heterocycl.Chem,1999,36(1),33-40.
157 Boullet,F.T.,Villemin,D.,Ricard,M.,Moison,H.,Foucaud,A.,Wittig,Wittig-Homer and Knoevenagel reactions by anionic activation with alumina or alumina-supported potassium fluoride in the absence of solvent,Tetrahedron,1985,41(7),1259-1266.
158 Ocampo,R.,Dolbier,W.R.,Synthesis of α,α-fluoro-β-lactones and their thermal conversion to 1-fluoroalkenes,Collect Czech Chem Commun,2002,67(9),1325-1334.
159 Ocampo,R.,Dolbier,W.R.,Synthesis of 1,1-difluoroalkenes via α-fluoro-β-lactones,J.Fluorine.Chem,1998,88(1),41-50.
160 Ocampo,R.,Dolbier,W.R.,A kinetic study of the thermal decarboxylation of α-fluoro-β-lactones,J.Org.Chem.,1997,62(1),109-114.
161 Hung,W.Y.,Lu,L.,Syudies on sulfinato-dehylgenation Ⅻ.Sodium dithionite-initiated addition of N,N-diethyliododifluoroacetamide to multiple bonds,Chinese Journal of Chemistry,1990,(1),68-74.
162 Sharpless,K.B.,Amberg,W.,Bennani,Y.L.,The osmium-catalyzed asymmetric dihydroxylation:a new ligand class and a process improvement,J.Org.Chem.,1992,57(10),2768-2771.
163 Bennani,Y.L.,Sharpless,K.B.,Asymmetric dihydroxylation(AD) of N,N-dialkyl and N-methoxy-N-methyl α,β- and β,γ-unsaturated amides,Tetrahedron Lett,1993,34(13),2079-2082.
164 Byun,H.S.,Kumar,E.R.,Bittman,R.,Enantioselective Syntheses of 1-O-Benzyl-sn-glycerol and 1-O-Hexadecyl-2-O-methyl-sn-glycerol via Asymmetric Dihydroxylation of Allyl 4-Methoxyphenyl Ether.Use of AD-Mix Supplemented with Potassium Persulfate,J.Org.Chem.,1994,59(9),2630.
165 张生勇,孙晓莉,李晓哗,对位取代的1,2-二苯基乙烯的合成及其不对称二羟基化反应,高等学校化学学报,1998,19(8),1227-1230.
166 Moriarty,R.M.,Zhuang,H.,Penmasta,R.,et.al,Inversion of configuration of α-trisubstituted(neopentyl) type secondary alcohols,Tetrahedron Lett,1993,34(50),8029-8032.
167 Huang,L.,Zhao,Y.,Yuan,L.,Min,J.,Zhang,L.,Syntheses and calcium-mobilizing evaluations of N1-glycosyl-substituted stable mimics of cyclic ADP-ribose,J.Med.Chem,2002,45(24),5340-5352.
168 Soengas,R.G.,Estevez,J.C.,Estevez,R.J.,Stereocontrolled transformation of nitrohexofuranoses into cyclopentylamines via 2-oxabicyclo[2.2.1]heptanes:incorporation of polyhydroxylated carbocyclic β-amino acids into peptides,Org.Lett.,2003,5(9),1423-1425.
169 Pak,C.S.,Lee,G.H.,Total synthesis of(+)-preussin,a novel antifungal agent,J Org.Chem.,1991,56(3),1128-1133.
170 Bhat,B.,Swayze,E.E.,Wheeler,P.,Dimock,S.,Perbost,M.,Sanghvi,Y.S.Synthesis of novel nucleic acid mimics via the stereoselective intermolecular radical coupling of 3'-iodo nucleosides and formaldoximes,J.Org.Chem.,1996,6(23),8186-8199.
171 杨少荣,胡先明,手性醇类化合物的构型反转,化学试剂,2001,23(1),15-20.
172 陈立仁,蒋生祥,刘霞,侯经国,高效液相色谱基础与实践,科学出版社,北京,2001,13.
2马红敏,邵瑞链,马治华,成俊然,动力学拆分法研究进展,有机化学,2000,20(4),454-463.
3 Victor,B.,Martin,S.,Sharpless,K.B.,Kinetic resolution of racemic allylic alcohols by enantioselective epoxidation.A route to substances of absolute enantiomeric purity? J.Am.Chem.Soc.,1981,103(20),6237-6240.
4 Vedejs,E.,Jure,M.,Efficiency in nonenzymatic kinetic resolution,Angew.Chem.Int.Ed.,2005,44(26),3974-4001.
5 Dalko,P.I.,Moisan,L.,In the gloden age of organocatalysis,Angew.Chem.Int.Ed,2004,43(39),5138-5175.
6 Vedejs,E.O.,Daugulis.O.,Diver,S.T.,Enantioselective acylations catalyzed by chiral phosphines,J.Org.Chem.,1996,61(2),430-431.
7 Vedejs.E.,Daugulis.O.,Tuttle.N.,Desymmetrization of meso-hydrobenzoin using chiral,nucleophilic phosphine Catalysts,J.Org.Chem.,2004,69(4),1389-1392.
8 Vedejs.E.,Daugulis.O.,2-Aryl-4,4,8-trimethyl-2-phosphabicyclo[3.3.0]octanes:reactive chiral phosphine catalysts for enantioselective acylation,J.Am.Chem.Soc.,1999,121(24),5813-5814.
9 Vedejs,E.,Dauglis.A.,Comparison of monocyclic and bicyclic phospholanes as acyl-transfer catalysts,J.Org.Chem.,2003,68(13),5020-5027.
10 Vedejs,E.,Daugulis,O.,A highly enantioselective phosphabicyclooctane catalyst for the kinetic resolution of benzylic alcohols,J.Am.Chem.Soc.,2003,125(14),4166-4173.
11 Vedejs,E.,Mackay,J.A.;Kinetic resolution of allylic alcohols using a chiral phosphine catalyst, Org. Lett., 2001,5(4), 535-536.
12 Jarvo, E.R., Copeland, G T., Papaioannou, N., Bonitatebus, P. J., Miller, S. J., Abiomimetic approach to asymmetric acyl transfer catalysis, J. Am. Chem. Soc.,1999, 121(50), 11638-11634.
13 Vasbinder, M. M., Jarvo, E. R., Miller, S. J., Incorporation of peptide isosteres into enantioselective peptide-based catalysts as mechanistic probes, Angew. Chem.Int. Ed, 2001, 40(15), 2824-2827.
14 Fierman, M. B., O'Leary, D. J., Steinmetz, W. E., Miller, S. J., Structure-selectivity relationships and structure for a peptide-based enantioselective acylation catalyst, J. Am. Chem. Soc, 2004,126(22), 6967-6971.
15 Copeland, G. T., Jarvo, E. R., Miller, S. J., Minimal acylase-like peptides.conformational control of absolute stereospecificity, J. Org. Chem., 1998, 63(20),6784-6785.
16 Copeland, G. T., Miller, S. J., Selection of enantioselective acyl transfer catalysts from a pooled peptide library through a fluorescence-based activity assay: an approach to kinetic resolution of secondary alcohols of broad structural scope, J.Am. Chem. Soc, 2001, 123(27), 6494-6502.
17 Jarvo, E. R., Evans, C. A., Copeland, G. T., Miller, S. J., Fluorescence-based screening of asymmetric acylation catalysts through parallel enantiomer analysis.Identification of a catalyst for tertiary alcohol resolution, J. Org. Chem., 2001,66(16), 5522-5527.
18 Copeland, G. T., Miller, S. J., A chemosensor-based approach to catalyst discovery in solution and on solid support, J. Am. Chem. Soc, 1999, 727(17),4306-4307.
19 Terakado, D., Koutaka, H., Oriyama, T. Organocatalytic kinetic resolution of racemic primary alcohols using a chiral 1,2-diamine derived from (S)-proline,Tetrahedron: Asymmetry, 2005,16(6), 1157-1165,.
20 Oriyama, T., Hori, Y., Imai, K., Sasaki, R., Nonenzymic enantioselective acylation of racemic secondary alcohols catalyzed by a SnX2-chiral diamine complex, Tetrahedron Lett, 1996, 57(47), 8543-8546.
21 Sano, T., Imai, K., Ohashi, K., Oriyama, T., Catalytic asymmetric acylation of racemic secondary alcohols with benzoyl chloride in the presence of a chiral diamine, Chem. Lett, 1999, (3), 265-266.
22 Vedejs, E., Chen, X., Kinetic resolution of secondary alcohols. Enantioselective acylation mediated by a chiral (dimethylamino)pyridine derivative, J. Am. Chem.Soc, 1996,118(7), 1809-1810.
23 Vedejs, E., Chen, X., Parallel kinetic resolution, J. Am. Chem. Soc, 1997,119(10), 2584-2585.
24 Ruble, J. C, Tweddell, J., Fu, G. C, Kinetic resolution of arylalkylcarbinols catalyzed by a planar-chiral derivative of DMAP: A new benchmark for nonenzymic acylation, J. Org. Chem., 1998, 63(9), 2794-2795.
25 Ruble, J. C, Latham, H. A., Fu, G. C., Effective kinetic resolution of secondary alcohols with a planar-chiral analog of 4-(dimethylamino)pyridine. Use of the Fe(C_5Ph_5) group in asymmetric catalysis, J. Am. Chem. Soc, 1997, 119(6),1492-1493.
26 Fu, G. C., Asymmetric catalysis with "planar-chiral" derivatives of 4-(dimethyl-amino)pyridine,Acc. Chem. Res., 2004, 57(8), 542-547.
27 Spivey, A. C., Arseniyadis, S., Fekner, T., Maddafordb, A., Leeseb, D. P., Rapid,room-temperature acylative kinetic resolution of sec-alcohols using atropisomeric 4-aminopyridine/triphenylphosphine catalysis, Tetrahedron, 2006,62(2-3), 295-301.
28 Spivey, A. C., Leese, D. P., Zhu, F., et.al, New atropisomericbiaryl derivatives of 4-aminopyridine identification of an improved nucleophilic catalyst for asymmetric acylation of sec-alcohols, Tetrahedron, 2004, 60(20), 4513-4525.
29 Spivey, A. C., Fekner, T., Spey, S. E., Axially chiral analogues of 4-(dimethylamino)pyridine: novel catalysts for nonenzymatic enantioselective acylations,J.Org.Chem.,2000,65(10),3154-3159.
30 Spivey,A.C.,Fekner,T.,Spey,S.E.,Adams,H.,Configurationally stable biaryl analogues of 4-(dimethylamino)pyridine:A novel class of chiral nucleophilic catalysts,J.Org.Chem.,1999,64(26),9430-9443.
31 Kawabata,T.,Nagato,M.,Takasu,K.,Fuji,K.,Nonenzymic kinetic resolution of racemic alcohols through an "Induced Fit" process,J.Am.Chem.Soc.,1997,119(13),3169-3170.
32 Kawabata,T.,Yamamoto,K.,Momose,Y.,Yoshida,H.,Nagaoka,Y.,Fuji,K.,Kinetic resolution of amino alcohol derivatives with a chiral nucleophilic catalyst:access to enantiopure cyclic cis-amino alcohols,Chem.Commun.,2001,(24),2700-2701.
33 Birman,V.B.,Li,X.,Benzotetramisole:A remarkably enantioselective acyl transfer catalyst,Org.Lett.,2006,8(7),1351-1354.
34 Birman,V.B.,Li,X.,Jiang,H.,Uffman,E.W.,Influence of electronic and steric factors on 2,3-dihydroimidazo[1,2-a]pyridine-based enantioselective acylation catalysts,Tetrahedron,2006,62(2-3),285-294.
35 Birman,V.B.,Uffman,E.W.,Jiang,H.,Li,X.,Kibane,C.J.,2,3-Dihydro imidazo[1,2-a]pyridines:A new class of enantioselective acyl transfer catalysts and their use in kinetic resolution of alcohols,J.Am.Chem.Soc.,2004,126(39),12226 -12227.
36 Birman,V.B.,Guo,L.,Kinetic resolution of propargylic alcohols catalyzed by benzotetramisole,Org.Lett.,2006,8(21),4859-4861.
37 Birman,V.B.,Jiang,H.,Kinetic resolution of alcohols using a 1,2-dihydroimidazo[1,2-a]quinoline enantioselective acylation catalyst,Org.Lett.,2005,7(16),3445-3447.
38 Birman,V.B.,Li,X.,Homobenzotetramisole:an effective catalyst for kinetic resolution of aryl-cycloalkanols,Org.Lett.,2008,10(6),1115-1118.
39 Birman,V.B.,Jiang,H.,Li,X.M.,et.al,Kinetic resolution of 2-oxazolidinones via catalytic,enantioselective N-acylation,J.Am.Chem.Soc.,2006,128(20),6536-6537.
40 Yamada,S.,Misono,T.,Iwai,Y.,Masumizu,A.,Akiyama,Y.,New class of pyridine catalyst having a conformation switch system:asymmetric acylation of various sec-alcohols,J.Org.Chem.,2006,71(18),6872-6880.
41 Tao,B.,Ruble,C.,Hoic,D.A.,Nonenzymatic kinetic resolution of propargylic alcohols by a planar-chiral DMAP derivative:crystallographic characterization of the acylated catalyst,J.Am.Chem.Soc.,1999,121(21),5091-5092.
42 Priem,G.,Pelotier,B.,Macdonald,S.J.F.,et,al,The design of novel N-4'-pyridinyl-α-methyl proline derivatives as potent catalysts for the kinetic resolution of alcohols,J.Org.Chem.,2003,68(10),3844-3848.
43 Jones,G.B.,Shielding in organic synthesis,Tetrahedron,2001,57(38),7999-8016.
44 Meyer,E.A.,Castellano,R.K.,Diederich,F.,Interactions with aromatic rings in chemical and biological recognition,Angew.Chem.Int.Ed,2003,42(11),1210-1250.
45 Tsuzuki,S.,Mikami,M.,Yamada,S.,Origin of attraction,magnitude,and directionality of interactions in benzene complexes with pyridinium cations,J.Am.Chem.Soc.,2007,129(27),8656-8662.
46 Ma,J.M.,Dougherty,D.A.,The cation-л interaction,Chem.Rev.,1997,97(5),1303-1324
47 Gallivan,J.P.,Dougherty,D.A.,Cation-л interactions in structural biology,Proc.Natl.Acad.Sci.USA.,1999,96(17),9459-9464.
48 Minoux,H.,Chipot,C.,Cation-л interactions in proteins:can simple models provide an accurate description? J.Am.Chem.Soc.,1999,121(44),10366-10372.
49 Burley,S.K.,Petsko,G.A.,Amino-aromatic interactions in proteins,FEBS Lett,1986,203(2).139-143.
50 Verdonk,M.L.,Boks,G.J.,Kooijman,H.J.,Stereochemistry of charged nitrogen-aromatic interactions and its involvement in ligand-receptor binding,J.Comput.Aided.Mol.Des.,1993,7(2),173-182.
51 Sussman,J.L.,Harel,M.,Frolow,F.,Atomic structure of acetylcholinesterase from Torpedo califomica:a prototypic acetylcholine-binding protein,Science,1991,253(5022),872-879.
52 Cooper,C.E.,Jan,Y.L.,Ion channel genes and human neurological disease:recent progress,prospects,and challenges,Proc.Natl.Acad.Sci.USA.,1991,96(9),4759-4766.
53 Mccurdy,A.,Jimenez,L.,Stauffer,D.,Dougherty,D.,Biomimetic catalysis of S_N2 reactions through cation-л interactions.The role of polarizability in catalysis,J.Am.Chem.Soc.,1992,114(26),10314-10321.
54 Favre,I.,Moezydlowski,E.,Schild,L.,Biomimetic catalysis of S_N2 reactions through cation-л interactions.The role of polarizability in catalysis,J.Gen.Physiol.,1995,106(26),10314-10321.
55 Bradley,M.,Bucheler,U.S.,Walsh,C.T.,Redox enzyme engineering:conversion of human glutathione reductase into a trypanothione reductase.Biochemistry,1991,30(25),6124-6127.
56 Walther.H.,The sensitizing action of hematoporphyrin,Biochemische Zeitschrift,1911,30,276-317.
57 Henderson,G.B.,Murgolo,N,J.,Engineering the substrate specificity of glutathione reductase toward that of trypanothione reduction,Proc.Natl.Acad.Sci.USA.,1991,88(19),8769-8773.
58 Adak,S.,Mazumder,A.,Bancrjee,R.K.,Probing the active site residues in aromatic donor oxidation in horseradish peroxidase:involvement of an arginine and a tyrosine residue in aromatic donor binding,Biochem.J.,1996,314(3),985-991.
59 Lakshminarasimhan,P.,Sunoj,R.B.,Chandrasekhar,J.,Ramamurthy,V. Cation-л interaction controlled selective geometric photoisomerization of diphenylcyclopropane,J.Am.Chem.Soc.,2000,122(19),4815-4816.
60 Mccurdy,A.,Jimenez,L.,Stauffer,D.,Dougherty,D.,Biomimetic catalysis of S_N2 reactions through cation-л interactions.The role of polarizability in catalysis,J.Am.Chem.Soc.,1992,114(26),10314-10321.
61 Yamada,S.,Saitoh,M.,Misono,T.,Stereoselective synthesis of 1,2- and 1,4-dihydropyridines by using cation-л interaction as a conformation-controlling tool,Tetrahedron Lett,2002,43(33),5853-5857.
62 Yamada,S.,Morita,C.,Face-selective addition to a cation-л complex of a pyridinium salt:synthesis of chiral 1,4-dihydropyridines,J.Am.Chem.Soc.,2002,124(28),8184-8185.
63 Yamada,S.,Uematsu,N.,Yamashita,K.,Role of cation-л interactions in the photodimerization of trans-4-Styrylpyridines,J.Am.Chem.Soc.,2007,129(40),12100-12101.
64 Yamada,S.,Yamamoto,J.,Ohta,E.,Enantioselective cyclopropanation reaction using a conformationally fixed pyridinium ylide through a cation-л interaction,Tetrahedron Lett,2007,48(5),855-858.
65 Lei,Y.,Jeffrey,A.,Cation-л control of regiochemistry of intramolecular schmidt reactions en route to bridged bicyclic lactams,J.Am.Chem.Soc.,2007,129(10),2766-2767.
66 Katz,C.E.,Ribelin T.,Withrow,D.,et.al,Nonbonded,attractive cation-лinteractions in azide-mediated asymmetric ring expansion reactions,J Org.Chem.,2008,73(9),3318-3327.
67 Huang,T.B.,Wang,K.,Liu,L.F.,He,F.H.,Insertion of((di-iso-propyl)amino)(chloro)phosphenium cation into phenylcyclopropane ring:stereochemistry,regioselectivity and mechanism,Main Group Chemistry,1999,3(1),5-14.
68 Kaanumalle,L.S.,Sivaguru,J.,Arunkumar,N.,et.al,Cation-л interactions as a tool to enhance the power of a chiral auxiliary during asymmetric photoreactions within zeolites,Chem.Cummun.,2003,(1),116-117.
69 Natarajan,A.,Ramamurthy,V.,Asymmetric induction during photocyclization of chiral and achiral α -oxoamides within achiral zeolites,Org.Biomol.Chem.,2006,4(24),4533-4542.
70 Bremer,O.,Synthesis of nitrated 2,3-dihydropyrimidazoles,annalen,1936,521,286-297.
71 Copp,F.C.,Timmis,G.M.,Potential tumor inhibitors.Esters of 4-di(2-hydroxy -ethyl)aminopyridine and quaternary derivatives of 2,3-dihydroglyoxalino [1,2-a]pyridine,J..Chem.Soc.,1955,2021-2027.
72 Weiner,N.,Kaye,I.,N-2-Pyridylalkanolamines and esters,J.Org.Chem.,1949,14(5),868-872.
73 Gomtsyan,A.,Bayburt,E.K.,Schmidt,R.G.,et.al.Novel transient receptor potential vanilloid 1 receptor antagonists for the treatment of pain:Structureactivity relationships for ureas with quinoline,isoquinoline,quinazoline,phthalazine,quinoxaline,and cinnoline moieties,J..Med Chem,2005,48(3),744-752.
74 李再峰,罗富英,N-芳基-N'-取代噻唑基脲的合成与结构表征,化学研究与应用,2001,13(1),80-82.
75 Gregory,R.J.H.,Cyanohydrins in nature and the laboratory:biology,preparations,and synthetic applications,Chem.Rev.,1999,99(12),3649-3682.
76 Effenberger,F.,Synthesis and reactions of optically active cyanohydrins.Angewandte Chemie,1994,106(15/16),1609-1619.
77 Michael,N.,Catalytic asymmetric cyanohydrin synthesis,SynLett,1993,(11),807-820.
78 Herranz,R.,Castro-Pichel,J.,and Garcia-Lopez,T.,Tributyltin cyanide,a novel reagent for the stereoselective preparation of 3-amino-2-hydroxy acids via cyanohydrin intermediates,Synthesis,1989,(9),703-6.
79 Garcia,M.M.C.,Ruano,J.L.G.,Highly stereoselective hydrocyanation of optically pure α-sulfinyl aldehydes,Tetrahedron:Asymmetry,1998,9(5),859-864.
80 Terashima,S.,Synthesis of optically active and biologically active compounds,Synlett,1992,(9),691-702.
81 Golinski,M.,Brock,C.P.,Watt,D.,S.,Addition of tert-butyldimethyl- or tert-butyldiphenylsilyl cyanide to hindered ketones,J.Org.Chem.,1993,58(1),159-164.
82 Effenberger,F.,Gutterer,B.,Ziegler,T.,Enzyme-catalyzed reactions.7.Enantioselective esterification of racemic cyanohydrins and enantioselective hydrolysis or transesterification of cyanohydrin esters by lipases,Liebigs.Ann.Chem,1991,(1),47-54.
83 Hsu,S.H.,Wu,S.H.,Wang,Y.F.,Wong,C.H.,Lipase-catalyzed irreversible transesterification using enol esters:XAD-8 immobilized lipoprotein lipasecatalyzed resolution of secondary alcohols,Tetrahedron Lett.,1990,31(44),6403 -6406.
84 Inagaki,M.,Hiratake,J.,Nishioka T.,Oda,J.,Lipase-catalyzed kinetic resolution with in situ racemization:one-pot synthesis of optically active cyanohydrin acetates from aldehydes,J.Am.Chem.Soc.,1991,113(24),9360-9361.
85 Inagaki,M.,Hiratake,J.,Nishioka,T.,Oda,J.,One-pot synthesis of optically active cyanohydrin acetates from aldehydes via lipase-catalyzed kinetic resolution coupled with in situ formation and racemization of cyanohydrins,J..Org.Chem.,1992,57(21),5643-5649.
86 Ohta,H.,Miyamae,Y.,Tsucchihashi,G.,Asymmetric hydrolysis of aryloxyacetaldehyde cyanohydrin acetates,Argric.Biol.Chem.,1986,50(12),3181-3184.
87陈沛然,手性氰醇化合物的生物催化合成及其应用于生物活性分子合成中的研究,中国科学院上海有机化学研究所博士论文,2003,133-208.
88 Date,J.,Dull,D.,Mosher,H.,α-Methoxy-α-trifluoromethylphenylacetic acid,a versatile reagent for the determination of enantiomeric composition of alcohols and amines,J.Org.Chem.,1969,34(9),2543-2549.
89 Mendez,E.,Brieva,R.,Rebolledo,F.,Gotor,V.,Optically active(S)-ketone- and (R)-aldehyde-cyanohydfins via an(R)-oxynitrilase-catalyzed transcyanation.Chemoenzymic syntheses of 2-cyanotetrahydrofuran and 2-cyanotetra -hydropyran,J.Chem.Soc.,Chem.Commun.,1995,(10),989-990.
90 Effenberger,F.,Ziegler,T.,Forster,S.,Enzyme-catalyzed cyanohydrin preparation in organic solvents,Angewandte Chemie,1987,99(5),491-492.
91 Brussee,J.,Roos,E.C.,van der Gen,A.,Bioorganic synthesis of optically active cyanohyddns and acyloins,Tetrahedron Lett.,1988,29(35),4485-4488.
92 Brussee,J.,Loos,W.T.,Kruse,C.G.,van der Gen,A.Synthesis of optically active silyl protected cyanohydrins,Tetrahedron,1990,46(3),979-986.
93 Gerrits,P.J.,Zumbragel,F.,Marcus,J.,Analyzing the hydrocyanation reaction:chiral HPLC and the synthesis of racemic cyanohydrins,Tetrahedron,2001,57(41),8691-8698.
94 Belokon,Y.N.,Blacker,A.J.,Carta,P.,et.al,Synthetic and mechanistic studies on asymmetric cyanohydrins synthesis using a titanium(salen) bimetallic catalyst,Tetrahedron,2000,60(46),10433-10447.
95 Gokel,G.W.,Wall,S.L.D.,Meadow,E.S.,Experimental evidence for alkali metal cation-л interactions,Eur.J.Org.Chem.,2000,(17),2967-2978.
96 Tsuzuki,S.,Mikami,M.,Yamada S.,Origin of attraction,magnitude,and directionality of interactions in benzene complexes with pyridinium cations,J.Am.Chem.Soc.,2007,129(27),8656-8662.
97 Yamada,S.,Misono,T.,Tsuzuki,S.Cation-л interactions of a thiocarbonyl group and a carbonyl group with a pyridinium nucleus,J.Am.Chem.Soc,2004,126(31),9862-9872.
98 卿凤翎,高文忠,钯催化下(Z)-3-碘-3-三氟甲基-1-芳基烯丙醇与末端炔烃的 偶联反应,有机化学,2000,20(5),764-765.
99 Cristiane,P.,Mariada Grace,N.,Effects of organic solvents and ionic liquids on the aminolysis of(RS)-methyl mandelate catalyzed by lipases,Tetrahedron:Asymmetry,2006,17(3),428-433.
100 Zhao,H.T.,Qin,B.,Liu,X.H.,Feng,X.M.,Enantioselective trifluoromethylation of aromatic aldehydes catalyzed by combinatorial catalysts,Tetrahedron,2007,63(29),6822-6826.
101 Steele,R.M.,Monti,C.,Gennari,C.,et.al,Enantioselective cyanosilylation of aldehydes catalysed by a diastereomedc mixture of atropisomedc thioureas,Tetrahedron:Asymmetry,2006,17(6),999-1006.
102 Schmidt,M.,Herve',S.,Klempier,N.,Griengl,H.,Preparation of optically active cyanohydrins using the(S)-hydroxynitrile lyase from Hevea brasiliensis,Tetrahedron,1996,52(23),7833-7840.
103 Iseki,K.,Catalytic asymmetric synthesis of chiral fluoroorganic compounds,Tetrahedron,1998,54(46),13887-13914.
104 卿凤翎,邱小龙,“有机氟化学'2007,科学出版社,北京,317-349.
105 Ma,J.,Cahard,D.,Asymmetric fluorination,trifluoromethylation,and perfluoroalkylation reactions,Chem.Rev.,2004,104(12),6119-6146.
106 Gelb,M.H.,Fluoro ketone phospholipid analogs:new inhibitors of phospholipase A2,J.Am.Chem.Soc.,1986,108(11),3146-3147.
107 Jimenez,O.,Bosch,M.P.,Guerrero,A.,Practical and efficient synthesis of alkyl,alkenyl and aryl-alkyl α,α-difluoro esters as precursors of potential inhibitors of the pheromone catabolism in insects,Synthesis,2000,(13),1917-1924.
108 彭荣达,郝健,含氟β-氨基酸及其衍生物的合成进展,有机化学,2005,25(5),485-495.
109 Fokina,N.A.,Kornilov,A.M.,Kukhar,V.P.,The Mitsunobu reaction in the synthesis of α,α-difluoro-β-amino acids,J.Fluorine.Chem.,2001,111(1),69-76.
110 Kuroki,Y.,Asada,D.,Iseki,K.,Enantioselective synthesis of 2,2-difluoro 3-hydroxy carboxylates by rhodium-catalyzed hydrogenation,Tetrahedron Lett.,2000,41(50),9853-9858.
111 Kloetzing,R.J.,Thaler,T.,Knochel,P.,An improved asymmetric reformatsky reaction mediated by(-)-N,N-dimethylaminoisoborneol,Org.Lett.,2006,8(6),1125-1128.
112 Andre,J.M.,Martinez,M.A.,Pedrosa,R.,Perez-Encabo,A.Synthesis of chiral α,α-difluoro β-hydroxy esters by enantioselective Reformatskii reaction,Synthesis,1996,(9),1070-1072.
113 Iseki,K.,Kuroki,Y.,Asada,D.,Kobayashi,Y.Isolation of α,α-difluoroketene silyl acetal and its application to asymmetric aldol reactions,Tetrahedron Lett.,1997,.38(8),1447-1448.
114 Iseki,K.,Kuroki,Y.,Asada,D.,Takahashi,M.,Kishimoto,S.,Kobayashi,Y.,Asymmetric aldol addition of aldehydes to a difluoroketene silyl acetal catalyzed by chiral Lewis acids,Tetrahedron,1997,53(30),10271-10280.
115 Linderman,R.J.,Graves,D.M.,Oxidation of fluoroalkyl-substituted carbinols by the Dess-Martin reagent,J.Org.Chem.,1989,54(3),661-668.
116 Fukuda,H.,Kitazume,T.A.,General route to N'-(2,2-difluoro-3-hydroxy alkanoyl)nornicotines,J.Fluorine.Chem,1995,74(2),171-176.
117 Meadows,E.S.,Wall,S.L.D.,Barbour,L,J.,Gokel,G.W.,Alkali metal Cation-π interaction observed by using a lariat ether model system,J.Am.Chem.Soc.,2001,123(13),3092-3107.
118 Ngola,S.M.,Dougherty,D.A.,Concerning the effects of aromatic ring fluorination on the Cation-π interaction and other molecular recognition phenomena in aqueous media,J.Org.Chem.,1998,63(14),4566-4567.
119 黄贤海,施国强,有机分子中引入二氟亚甲基的最新进展,有机化学,1997,17(5),394-410.
120 Berkiwitz,D.B.,Sloss,D.G.,Diallyl(lithiodifluoromethyl)phosphonate:A new reagent for the introduction of the(difluoromethylene)phosphonate functionality,J.Org.Chem.,1995,60(21),7047-7050.
121 Matulic-Adamic,J.,Haeberli,P.,Usman,N.,Synthesis of 5'-deoxy-5'-difluoromethyl phosphonate nucleotide analogs,J.Org.Chem.,1995,60(8),2563-2569.
122 Schirlin,D.,Baltzer,S.,Altenburger,J.A.,Tarnus,C.,Remy,J.M.,Difluoromethylene-ketone retroamide,a versatile concept of inactivation of proteolytic enzymes,Tetrahedron,1996,52(1),305-318.
123 吴繁花,含氟γ-内酯的合成研究,华东理工大学博士论文,2005.
124 Watanabe,K.A.,Reichman,U.,Hirota,K.,Lopez,C.,Fox,J.J.,Nucleosides.synthesis and antiherpes virus activity of some 2'-fluoro-2'-deoxyarabino furanosyl pyrimidine nucleosides,J.Med.Chem,1979,22(1),21-24.
125 Etzold,G.,Hintsche,R.,Kowollik,G.,Langen,P.,Nucleosides of fluoro sugars.Ⅵ.Synthesis and reactivity of 3'-fluoro-and 3'-chloro-3'-deoxythymidine,Tetrahedron,1971,2 7(12),2463-2472.
126 Balzarini,J.,Baba,M.,Pauwells,R.,Herdewijn,P.,De Clercq,E.,Anti-retrovirus activity of 3'-fluoro- and 3'-azido-substituted pyrimidine 2',3'-dideoxynucleoside analogs,Biochem.Pharmacol,1988,37(14),2847-2856.
127 Hertel,L.W.,Kroin,J.S.,Misner,J.W.,Tustin,J.M.,Synthesis of 2-deoxy-2,2-difluoro-D-ribose and 2-deoxy-2,2'-difluoro-D-ribofuranosyl nucleosides,J.Org.Chem,1988,53(11),2406-2409.
128 Toshiyuki,I.,Kazutoshi,K.,Kazuhisa,Y.,et.al,Synthesis and biological activity of point-fluorinated pheromone analogues of Eldana saccharina,Eur.J.Org.Chem.,2004,(2),406-412.
129 Toshiyuki,T.,Kohei,S.,Kazutoshi,K.,Asymmetric synthesis of both enantiomers of α,α-difluoroeldanolide an interesting property of their biological activity,Tetrahedron Lett.,1998,39(23),4071-4047.
130 Pankiewicz,K.W.,Fluorinated nucleosides,Carbohydr.Res,2000,327(1-2), 87-105.
131 Fuchigami,T.,Fujita,T.,Electrolytic partial fluorination of organic compounds.14.The first electrosynthesis of hypervalent iodobenzene difluoride derivatives and its application to indirect anodic gem-difluorination,J.Org.Chem.,1994,59(24),7190.
132 Ogura,K.,Ogu,K.,Ayabe,T.,et.al,Stereoselective formation of a-fluoro-a-trifluoromethyl-g-lactones starting from γ-hydroxy-α,β-unsaturated sulfones and a hexafluoropropene-diethylamine adduct(PPDA),Tetrahedron Lett,1997,38(29),5173-5176.
133 Okada,M.,Nakamura,Y.,Horikawa,H.,et.al,Fluoro-lactonization of 4-alkenoic acid derivatives with N-fluoropentachloropyridinium triflate,J.Fluorine.Chem,1997,82(2),157-161.
134 Sawaguchi,M.,Hara,S.,Fukuhara,T.,Yoneda,N.,Fluorocyclization of unsaturated alcohols and carboxylic acids by iodotoluene difluoride and amine-HF complexes,J.Fluorine.Chem,2000,104(2),277-280.
135 Ramachandran,P.V.,Padiya,K.J.,Rauniyar,V.,Reddy,M.V.R.,Brown,H.C.,Asymmetric synthesis of γ-perfluoroalkyl(aryl)butyrolactones via organoboranes,Tetrahedron Letters,2004,45(5),1015-1017.
136 Naddaka,V.,Klopfer,E.,Saeed,S.,et.al,Process for preparing gemcitabine and associated intermediates,W.O Pat 2007070804 A2,2007.
137 Kim,M.S.,Kim,Y.J.,Choi,J.H.,et.al,A manufacturing process of 2',2'-difluronucleoside and intermediate,W.O Pat 2007069838 A1,2007.
138 Palle,V.,Raghavendra,A.,Nariyam,S.M.,et.al,Preparation of gemcitabine,W.O Pat 2007117760 A2,2007.
139 Kotra,L.P.,Xiang,Y.J.,Newton,M.G.,Schinazi,R.F.,et.al,Structureactivity relationships of 2'-deoxy-2',2'-difluoro-1-erythro-pentofuranosyl Nucleosides,J.Med.Chem,1997,40(22),3635-3644.
140 Bravo,P.,Frigerio,M.,Melloni,A.,et.al,Stereoselective synthesis of both enantiomers of trifluoro-valcrolactone and Pentafluro-caprolactone,Eur.J.Org.Chem.,2002,(12):1895-1902.
141 Ge,P.,Kirk,K.L.,Synthesis of 2-deoxy-2-halo-L-ascorbic acids,J.Org.Chem.,1997,62(10),3340-3343.
142 Xiao,F.H.,Wu,F.H.,Shen,Y.J.,Zhou,L.F.,Synthesis of α,α-difluoro-γ-butyrolactones via ethyl iododifluoroacetate,J.Fluorine.Chem,2005,126(1),63-67.
143 李纪国,孙曙光,张正,相转移催化法制苄醚,化学试剂,1986,8(6),370-371.
144 Zhao,G.,Sun,H.L.,Cp_2TiCl_2(cat)/Zn system promoted addition reaction of bromo-difluoro acetate with the election-deficient gem-dicyanoalkenes,J.Fluorine.Chem,2001,111(2),217-219.
145 Yang,Z.Y.,Burton,D.J.,A novel and practical method for the preparation of α,α-difluorofunctionalized esters,J.Chem.Soc,Chem.Commun.,1992,(3)233-234.
146 Yang,Z.Y.,Burton,D.J.,Nickel-catalyzed reaction of iododifluoroacetates with alkenes and zinc:A novel and practical route to α,α-difluoro-functionalized esters and α,α,ω,ω-tetrafluoro diesters,J.Org.Chem.,1992,57(19),5144-5149.
147 Yang,Z.,Burton,D.,A new approach to α,α-difluoro-functionalized esters,J.Org.Chem.,1991,56(17),5125-5132.
148 Murakami,S.,Ishii,H.,Fuchigami,T.,Eletrosynthesis of ethyl α,α-difluoro-α-(phenylseleno)acetate and its photochemical synthetic application,J.Fluorine Chem,2004,125(4),609-614.
149 Sato,K.,Omote,M.,Ando,A.,Kumadaki,A.I.,Reaction of ethyl bromodifluoroacetate in the presence of copper powder,J.Fluorine.Chem.,2004,125(4),509-515.
150 Schwaebe,M.K.,Mccarthy,J.R.,Whitten,J.P.,Nickel(0)-catalyzed coupling of vinylzirconiums to α-bromo-α,α-difluoro esters.Convenient generation of a functionalized allyldifluoro moiety,Tetrahedron Lett.,2001,41(6),791-794.
151 余审义,陈馥衡,Ando催化剂的发现、研究及催化机理,化学试剂,1999,21,(5),290-293.
152 Yadav,V.K.,Kapoor,K.K.,KF Adsorbed on alumina effectively promotes the epoxidation of electron deficient alkenes by anhydrous t-BuOOH,Tetrahedron,1996,52(10),3659-3668.
153 Alloum,B.A.,Villemin,D.,Potassium fluoride on alumina:an easy preparation of diazo carbonyl compounds,Synth.Commun,1989,19(13-14),2567-2671.
154 Kabalka,G.W.,Wang,L.,Namboodiri,V.,Pagni,R.M.,Rapid microwave-enhanced,solventless Sonogashira coupling reaction on alumina,Tetrahedron Lett,2000,41(27),5151-5154.
155 Kabalka,G.W.,Pagni,R.M.,Hair,C.M.,Solventless suzuki coupling reactions on palladium-doped KF/Al_2O_3,Org.Lett.,1999,1(9),1423-1425.
156 Nakano,Y.,Shi,W.,Nishii,Y.,Igarashi,M.J.,Knoevenagel reaction of malononitrile with methyl ketones followed by double cyclization catalyzed by potassium fluoride-coated alumina,Heterocycl.Chem,1999,36(1),33-40.
157 Boullet,F.T.,Villemin,D.,Ricard,M.,Moison,H.,Foucaud,A.,Wittig,Wittig-Homer and Knoevenagel reactions by anionic activation with alumina or alumina-supported potassium fluoride in the absence of solvent,Tetrahedron,1985,41(7),1259-1266.
158 Ocampo,R.,Dolbier,W.R.,Synthesis of α,α-fluoro-β-lactones and their thermal conversion to 1-fluoroalkenes,Collect Czech Chem Commun,2002,67(9),1325-1334.
159 Ocampo,R.,Dolbier,W.R.,Synthesis of 1,1-difluoroalkenes via α-fluoro-β-lactones,J.Fluorine.Chem,1998,88(1),41-50.
160 Ocampo,R.,Dolbier,W.R.,A kinetic study of the thermal decarboxylation of α-fluoro-β-lactones,J.Org.Chem.,1997,62(1),109-114.
161 Hung,W.Y.,Lu,L.,Syudies on sulfinato-dehylgenation Ⅻ.Sodium dithionite-initiated addition of N,N-diethyliododifluoroacetamide to multiple bonds,Chinese Journal of Chemistry,1990,(1),68-74.
162 Sharpless,K.B.,Amberg,W.,Bennani,Y.L.,The osmium-catalyzed asymmetric dihydroxylation:a new ligand class and a process improvement,J.Org.Chem.,1992,57(10),2768-2771.
163 Bennani,Y.L.,Sharpless,K.B.,Asymmetric dihydroxylation(AD) of N,N-dialkyl and N-methoxy-N-methyl α,β- and β,γ-unsaturated amides,Tetrahedron Lett,1993,34(13),2079-2082.
164 Byun,H.S.,Kumar,E.R.,Bittman,R.,Enantioselective Syntheses of 1-O-Benzyl-sn-glycerol and 1-O-Hexadecyl-2-O-methyl-sn-glycerol via Asymmetric Dihydroxylation of Allyl 4-Methoxyphenyl Ether.Use of AD-Mix Supplemented with Potassium Persulfate,J.Org.Chem.,1994,59(9),2630.
165 张生勇,孙晓莉,李晓哗,对位取代的1,2-二苯基乙烯的合成及其不对称二羟基化反应,高等学校化学学报,1998,19(8),1227-1230.
166 Moriarty,R.M.,Zhuang,H.,Penmasta,R.,et.al,Inversion of configuration of α-trisubstituted(neopentyl) type secondary alcohols,Tetrahedron Lett,1993,34(50),8029-8032.
167 Huang,L.,Zhao,Y.,Yuan,L.,Min,J.,Zhang,L.,Syntheses and calcium-mobilizing evaluations of N1-glycosyl-substituted stable mimics of cyclic ADP-ribose,J.Med.Chem,2002,45(24),5340-5352.
168 Soengas,R.G.,Estevez,J.C.,Estevez,R.J.,Stereocontrolled transformation of nitrohexofuranoses into cyclopentylamines via 2-oxabicyclo[2.2.1]heptanes:incorporation of polyhydroxylated carbocyclic β-amino acids into peptides,Org.Lett.,2003,5(9),1423-1425.
169 Pak,C.S.,Lee,G.H.,Total synthesis of(+)-preussin,a novel antifungal agent,J Org.Chem.,1991,56(3),1128-1133.
170 Bhat,B.,Swayze,E.E.,Wheeler,P.,Dimock,S.,Perbost,M.,Sanghvi,Y.S.Synthesis of novel nucleic acid mimics via the stereoselective intermolecular radical coupling of 3'-iodo nucleosides and formaldoximes,J.Org.Chem.,1996,6(23),8186-8199.
171 杨少荣,胡先明,手性醇类化合物的构型反转,化学试剂,2001,23(1),15-20.
172 陈立仁,蒋生祥,刘霞,侯经国,高效液相色谱基础与实践,科学出版社,北京,2001,13.