α-芳基丙酸选择性合成研究
|
摘要
α-芳基丙酸（α-arylpropanic acid）是一类广泛使用的非甾体抗炎药，其独特的解热、消炎和镇痛作用，越来越为人们所接受。特别是萘普生，由于它的疗效高，副作用小等优点，已成为药物市场的主流产品。但由于（R）-萘普生对肝脏的副作用大，现在人们普遍趋向于使用单一手性（S）-(+)-萘普生产品。
本论文优化了傅氏烷基化反应合成α-芳基丙酸的方法，用硝基甲烷和三乙胺分别
代替毒性大的硝基苯和吡啶，得到了满意的试验结果；并对三种烷基化试剂：对
甲苯磺酸乳酸乙酯、丙烯醇及环氧丙烷所进行的反应进行了研究对比。
本论文的另一创新之处是采用面包酵母对中间体：α-亚甲基苯乙酸乙酯、α-亚甲基苯乙氰和α-亚甲基苯乙酸分别进行还原，并对还原产物的种类及结构通过气质联用进行了分析，提出了合理的解释，而且针对三种前体的特点分别采用了Wittig-Horner反应、mannich反应和氰水解反应及卡宾法等合成方法，比较了各种合成途径，提出了一条简易合成α-亚甲基苯乙酸的方法，中间体主要通过红外光谱和核磁共振氢谱进行了表征。
α-arylpropanic acids have been proved to be of great use on some diseases－rheumatism and rheumatoid arthritis for its highly effect on inflammation,ache and fever as non-steroidal anti-inflammatory agent .they are widely used as antipyrotic, anodyne and acetanilide.Because it was investigated that most of (R)-α-arylpropanic acids have much negative effect on stomach， (S)- α-arylpropanic acids ,which chem- -ists are effort to synthesize pure optically active isomer ，are popular with patients.
The dissertation optimizes the condition of Friedel-Crafts reaction,using nitro- -methane and triethylamine instead of nitrobenzene and pyridine, respectively .The innovation of the paper is that Baker’s Yeast has been used to reduce a series of intermediate products of α-arylpropanic acids such as ethyl α-methylenebenzeneacetate , α-methylenebenzeneacetonitrile and α-methylenebenzeneacetic acid.The reduced products are analysed by GC-MS and given a rational explaination.Furthermore,serval ways to synthesizing intermediate products have been investigated , and a simple route to synthesizing α-methylenebenzeneacetic acid come through carbenes was been found.Most of the intermediate products have been characterized by IR and 1H-NMR.
本论文优化了傅氏烷基化反应合成α-芳基丙酸的方法，用硝基甲烷和三乙胺分别
代替毒性大的硝基苯和吡啶，得到了满意的试验结果；并对三种烷基化试剂：对
甲苯磺酸乳酸乙酯、丙烯醇及环氧丙烷所进行的反应进行了研究对比。
本论文的另一创新之处是采用面包酵母对中间体：α-亚甲基苯乙酸乙酯、α-亚甲基苯乙氰和α-亚甲基苯乙酸分别进行还原，并对还原产物的种类及结构通过气质联用进行了分析，提出了合理的解释，而且针对三种前体的特点分别采用了Wittig-Horner反应、mannich反应和氰水解反应及卡宾法等合成方法，比较了各种合成途径，提出了一条简易合成α-亚甲基苯乙酸的方法，中间体主要通过红外光谱和核磁共振氢谱进行了表征。
α-arylpropanic acids have been proved to be of great use on some diseases－rheumatism and rheumatoid arthritis for its highly effect on inflammation,ache and fever as non-steroidal anti-inflammatory agent .they are widely used as antipyrotic, anodyne and acetanilide.Because it was investigated that most of (R)-α-arylpropanic acids have much negative effect on stomach， (S)- α-arylpropanic acids ,which chem- -ists are effort to synthesize pure optically active isomer ，are popular with patients.
The dissertation optimizes the condition of Friedel-Crafts reaction,using nitro- -methane and triethylamine instead of nitrobenzene and pyridine, respectively .The innovation of the paper is that Baker’s Yeast has been used to reduce a series of intermediate products of α-arylpropanic acids such as ethyl α-methylenebenzeneacetate , α-methylenebenzeneacetonitrile and α-methylenebenzeneacetic acid.The reduced products are analysed by GC-MS and given a rational explaination.Furthermore,serval ways to synthesizing intermediate products have been investigated , and a simple route to synthesizing α-methylenebenzeneacetic acid come through carbenes was been found.Most of the intermediate products have been characterized by IR and 1H-NMR.
引文
[1] 殷元骥,蒋耀忠，不对称催化反应进展，北京：科学出版社，2000
[2] 张伦.萘普生市场透析，中国制药信息，2002,18(8)：32~34
[3] 陈志龙，吴毓林，伍贻康，(S)-2-芳基丙酸不对称合成研究进展，有机化学，2002,22(1):22~32
[4] Nakajima,T.;Nakamoto,T.,Suga S,Asymmetric induction in the Friedel-Crafts reaction with (+)-1,2-epoxybutane and (-)-2-chloro-1-butanol, Bull Chem.Soc. Jpn,1975,48:960~965
[5] Orest Piccolo,Franca Spreafico ,Giuseppina visention,Zinc Salt Catalyzed Rearrangement of Acetal Optically Active Aryl1-Chloroethylketones:Synthesis of Optically Active 2-Arylpropionic Acids and Esters,J.org.Chem.,1987,52:10~14
[6] Piccolo O,Delgu G,Valoti E，Sterrespecific Friedel-Crafts alkylation of aronatic compounds:synthesis of optically active 2- and 3-arylalkanoic esters， J. Org. Chem, 1991,56:183~186
[7] Axel Brait,Hector Gonzalez,Patricia and Andy Y，Alkylation of 2- methoxynaphth
-alene with propylene oxide using titanium molecular sieves，Applied Catalysis A:General ,2000,194-195:265~273
[8] Fujii.K,Nakao.K,Yamauchi.T,Facile synthesis of alkyl 2-arylpropanoates from aryl ethyl ketones using lead(IV),synthesis,1982(6):456~457
[9] Tsuchihashi G,Oria,Honda Y，A General synthetic method of chiral 2-arylalkanoic esters via thermal 1,2-rearrangement，Bull chem Soc Jpn,1987, 60:1027~1036
[10] Castadldi G,Cavicchioll S,GiordandI C,et al，Tartaric acid,an efficient chiral auxiliary:new asymmetric synthesis of 2-alkyl-2-aryladtic acids，J. org .Chem,1987, 52:3018~3027
[11] 胡艾希，范国枝，赵海涛.消炎镇痛药萘普生不对称合成，药学学报,1999,34(4):290~292
[12] 刘湘，乔善宝，鲍明伟,等，S-萘普生的不对称合成，无锡轻工大学学报，2000，19（5）:500~502
[13] Tsuchihashi G，Synthesis of optically active 2-arylalkanioc acids by the use
of 1,2-rearrangment of the aryl group，Tetrahedron Lett,1981,22(43):4035~4038
[14] Peri,D, Wyandt, C M, Cleary, R.W, Hikal A H, Jones, A.B. Inclusion complexes of tolnaftate with β-cyclodextrin and hydroxypropyl β-cyclodextrin. Drug. Dev. Ind. Pharm. 1994,20,1401
[15] Kurono Masayasu,Toda Massaak,Nina Haruki,2-(4-Isobutylphenyl)propionic acid,Jp.P, 7753833,1977-04-30
[16] Kaoru Fuji,Manaba Node,Fujie Tanaka,et al,Binaphthol as a Chiral Auxillary Asymmetric Alaylation of Arylaceetic Acid Tetrahedron Lett,1989,30-:2825～2828
[17] Hirooyuki Isshibashi,Momoe Maeki,Junko Yagi,et al，A modification of the asymmetric dihyoxylation approach to the synthesis of (S)-2-arylpropanoic acids ，Tetrahedron,1999,55:6075~6080
[18]Hamon P G,Coghlan D R,Massy-Westropp R A,et al，Asymmetric synthesis of ibuprofen and ketoprofen ，Tetrahedron:Asymmetry, 1993,4(7): 1435~1438
[19] Thayashi ,N Kewamura，Asymmetric hydrogenation of trisubstituted acrylic acies catalyzed by a chiral (aminoalkyl) ferrocenylphosphine-Rhodium acie，J Am Chem Soc,1987,109:7876~7878
[20] 郭荷民，利用不对称交叉偶联反应合成（S）-(+)-萘普生，安徽大学学报（自然科学版），2002,26(2)：77~79
[21] J.D.Morrison,Asymmetric Synthesis(Vol5),New.York:Academic Press ,1985
[22] Dang T P,Kagan H B，Asymmetric synthesis of hydrotropic acid and amino acids by homogeneous catalytic hydyogenation，J .Chem .Soc:ChemCommun,1971,
(10):481~485
[23] Klobucar W.Dirk, Kolich Charles H,Manimanan,et al,Asymmetric hydrogenation of aromatic-substituted olefins using organoruthenium catalysts,U.S.P,5304524,
1994-04-19
[24] Frank R.Fronczek,G.Patrick Stahly,Thanlkavelu Manimaran,In Situ Generation of Ruthenium-Chiral Phosphine Complexes and Their Use in Asymmetric Hydrogenation, Organometalics,1993,12:1467~1470
[25] Pai Cheng Chao,Li Yue Ming ,Zhou Zhong Yuan,et al，Synthesis of new chiral diphosphine ligand (BisbenzodioxanPhos) and its application in asymmetric catalytic hydrogenation，Tetrahedron Lett,2002,43:2789~2792
[26] A Scrivant,U .Matteoli,A Convenient Synthesis of 2-(6-Methoxy-2-naphthyl- -propenoic Acid,Tetrahedron Lett,1995,36(49):9015~9018
[27] Harrison,IanT.,2-(1-Haloethyl)-6-methoxynaphthalenes,U.S.P,3652683, 1972-03-28
[28] Henri Arzoumanian,Gerard Buono,M’Barek Choukrad,et al,Asymmetric Carbonylation of 2-Methylbenzyl Bromide Catalyzed by Oxazaphospholane-Pall-
-adium Complexes under Phase-Transfer Condition,Organometalic,1988,7:59~62
[29] Zhou H Y,Cheng J,Lvsj,Fu H X,Wang H Q，Catalytic Carbonylation of α-(6-methoxyl-2-naphthyl)ethanol to methyl ester of naproxen using PdCl2-CuCl2-PPh3-acid catalyst system ，J Organomet Chem ,1998,556(1):239~242
[30] Eun Duck Park,KYung Hee Lee,Jae Sung Lee，Easily separable molecular catalysis,molecular catalysis:catalysis Today,2000,63：147~157
[31] 李岩云，夏春谷，PVP-PdCl2CuCl2/PPh3体系催化α-（6-甲氧基－2-萘基）乙醇羰化反应研究 ，分子催化，2001，15(2)：129~132
[32] Howard Alper,Nathalie Hamel,Asymmetric Synthesis of Acids by the Palladium-Catalyzed Hydrocarboxylation of Olefins in the Presence of (R)-(-)-or(S)-
(+)-1,1′-Binaphthyl-2,2′-diyl Hydrogen Phosphate,J.Am.Chem.Soc,1990,112:
2083~2084
[33] Baker G.L,Fritschel.S,Stille.K.J,Transition-metal catalyzed asymmetric organic synthesis via polymer-attached optically active phosphine ligand .6.Asymmetric hydrogenation with polymer catalysts containing optically active,pendent alcoh-
-ols,1981,46(14):2960~2965
[34] Rossi R .F, Heefner D. L，Enantioselective production of chiral carboxylic acids,
U.S.P,5 273 895 ,1993－12－28
[35] Garicam ,Delcampo C, Chemoenzymatic synthesis of pure enantiomeric arylpropanic acids ,Tetrahedron,1993,49(37):8433~8440
[36] Thanikavelu Manimaran,Patrick Stahly G,Optical purification of profen drugs,
Tetrahedron:Asymmetry,1993,4(8):1949~1954
[37] Marina Cretich,Marcella Chiari,GlacomoI Carrea,Stereselective synthesis of (S)-(+)-naproxen catalyzed by carboxyl esterase in a multicompartment electrolyzer, J Biochem Biophys Methods,2001,48:247~256
[38] Kenyon.J,Phillips.H,Turley.H.G,Dependence of rotatory power on chiral constitution .XXIV.Futher experiments on the Walden inversion J.Chem.Soc,
1925,127:399~417
[39 ] Tadashi Naka Jima,Yoshiaki Nakamoto,and Sohei Suga,Asymmeric Induction in Friedel-Crafts Reaction with (+)-1,2-Epoxybutane and(-)-2-Chloro--1-butanol, Bull-
-etinof the Chemcial Society of Japan,1975,48(3):960~965
[40] Shoji Kajiaeshi,Hiroshi Kawamukal,Shizuo Fujisaki,Oxidation Using Quaternary Ammonium Polyhalides.Ⅲ.An Effective Oxidation of Alcohols and Ether by the Use of Benzyltrimethylammonium Tribromide,Bull.Chem. Soc.Jpn, 1989,62:
2585~2588
[41] Takashi Morimoto,Masao Hirando,Takayoshi Hamaguchi et al,Oxidation of Alcohols with Peracetic Acid in Ethyl Acetate in the Presence of Sodium Bromide
,Bull Chem. Soc.Jpn,1992,65:703~706
[42] Hiroki Tomioka,Koichiro Oshima,Hitosi Nozaki,Cerium Cataiyzed Selective Oxidation of Secondary Alcohols in the The Presence of Primaryones,Tetrahedron Letters,1982,23(5):539~542
[43] Jean Villieras,Monique Rambaud,Wittig-Horner Reaction in Heterogeneous Media;V1.An Efficient Synthesis of α-Methylenecarboxylic Esters and α-Methyleneketone under Mild Conditions,Synthesis Communications,1984,406~408
[44] Jean Villieras,Monique Rambaud,Wittig-Horner Reaction in Heterogeneous Media;21.A Convenient Synthesis ofα,β-Unsaturated Esters and Kentones using Weak Bases in Water, Synthesis Communications,1983,300~303
[45] M.Finlay*,J.P.Debiard,A.Guy,D.Molko,R.Teoule,An Efficient One-Pot Synthesis of a Fully Protected 2’-Deoxytidine 3’-Monophosphate, Synthesis Communica-
-tions,1983,303~306
[46] N.S.Abramov and Shara Pall,Mechanism of the Arbuzov rearrangement. V.Reaction of ester of bromo substituted carboxylic acids with phosphates,Trudy Kazan. Khim.Tekhnol.Inst.im.S.M.Kirova,1957,23:105~110
[47] J.H.Boyer and D.Straw,Azidocarbonyl compounds.Ⅱ.The pyrolysis of α-azidocarbonyl compounds,J.Am.Chem.Soc,1953,75:1642~1644
[48] Lichty,nitriles of acrylic acids, U.S.P ,2208328,1940-6-16
[49] Joseph Frederic Walker,Westfield,N.J.,Willington,del.,Preparation of Atroponitrile,U.S.P.,2478990,1949-08-16
[50] Brant ,acrylonitriles,U.S.P.,2386586,1945-10-09
[51] Francisco S.Alvarez,Sunnyvale,Calif.,U.S.P.,3637767,1972-01-25
[52] 王清廉，沈凤嘉，有机化学实验（第二版），河北：高等教育出版社，1992.250~254
[53] Chan Albert S.C,Asymmetric catalytic hydrogenation of alpha-arylpropenic
acids ,U.S.P,4994607,1991-02-19
[54] Kunihiko Takabe, Hidetaka Hiyoshi, Hiroyuki Sawada et al. Stereochemistry of thiazolidine ring formation from aminals and cysteine Tetrahedron: Asymmetry, 1992, 3: 1399-1400.
[55]Yasushi Kawai, Motoko Hayashi, Yoshikazu Sawada et al. Asymmetric Reduction of α,β-Unsaturated Ketones with a Carbon-Carbon Double-Bond Reductase from Baker's Yeast Tetrahedron Lett., 1998, 39: 5225-5228
[56] Ezequias P Siqueria Filho, J Augusto R Rodrigues, Paulo J S Moran. Baker's yeast reduction of α-methyleneketones Tetrahedron: Asymmetry, 2001, 12: 847-852
[57] Patrizia Ferraboschi, Shahrzad Beza-Elahi, Elisa Verza et al. Baker's yeast mediated biohydrogenation of unsaturated compounds containing a methylene group: enantioselective preparation of 2-methyl alkanols from 2-substituted acrolein acetals Tetrahedron: Asymmetry, 1999, 10: 2639-2642
[58] Yasushi Kawai, Yoshikazu Inaba, Norihiro Tokitoh. Asymmetric reduction of nitroalke-nes with baker’s yeast Tetrahedron: Asymmetry, 2001, 12: 309-318.
[59] Biswabnath Das, A Kashinatham, P Madhusudhan. Baker’s yeast treatment of some naturally occurring amides Tetrahedron Lett., 1997, 38: 7457-7458
[60] Ahmed Kamal, K Venkata Ramana, Maddamsetty V Rao. Chemoenzymatic synthesis of pyrrolo[2,1-b]quinazolinones: Lipase-Catalyzed resolution of Vasicinone J. Org. Chem., 2001, 66: 997-1001
[61] Fronza G, Fufanti C, Grasselli P et al. Conversion of 4-oxy-substituted crotonaldehyde into 1-protected (2R)-1,2,4-butanetriol: a new synthetic capacity of bakers' yeast J. Org. Chem., 1988, 53: 6153-6154
[62] Fronza G, Fufanti C, Grasselli P et al,on the products obtained from γ-oxygen substituted crotonaldehyde in fermenting baker's yeast, Biocatalysis, 1990, 3: 51-54
[63] 赵桂枝，张卫东，李学良，以酒石酸酯为手性助剂不对称合成萘普生，沈阳医科大学学报，1998，15：193～195
[64] A.S.C.Chan*,T.T.Huang,J.H.Wagenknecht,and R.E.Miller,A Novel Synthesis of 2-ArylacticAcids via Electrocarboxylation of MethylArylKetone,J.org.Chem,1995,60:
742~744
[65] Francisco S.Alvarez,Sunnyvale,,Calif.，2-(6?-Methoxynaphth-2?-yl) Propylene-
-oxide and 5?-Halo Derivatives,U.S.P.,3637767,1972-01-25
[2] 张伦.萘普生市场透析，中国制药信息，2002,18(8)：32~34
[3] 陈志龙，吴毓林，伍贻康，(S)-2-芳基丙酸不对称合成研究进展，有机化学，2002,22(1):22~32
[4] Nakajima,T.;Nakamoto,T.,Suga S,Asymmetric induction in the Friedel-Crafts reaction with (+)-1,2-epoxybutane and (-)-2-chloro-1-butanol, Bull Chem.Soc. Jpn,1975,48:960~965
[5] Orest Piccolo,Franca Spreafico ,Giuseppina visention,Zinc Salt Catalyzed Rearrangement of Acetal Optically Active Aryl1-Chloroethylketones:Synthesis of Optically Active 2-Arylpropionic Acids and Esters,J.org.Chem.,1987,52:10~14
[6] Piccolo O,Delgu G,Valoti E，Sterrespecific Friedel-Crafts alkylation of aronatic compounds:synthesis of optically active 2- and 3-arylalkanoic esters， J. Org. Chem, 1991,56:183~186
[7] Axel Brait,Hector Gonzalez,Patricia and Andy Y，Alkylation of 2- methoxynaphth
-alene with propylene oxide using titanium molecular sieves，Applied Catalysis A:General ,2000,194-195:265~273
[8] Fujii.K,Nakao.K,Yamauchi.T,Facile synthesis of alkyl 2-arylpropanoates from aryl ethyl ketones using lead(IV),synthesis,1982(6):456~457
[9] Tsuchihashi G,Oria,Honda Y，A General synthetic method of chiral 2-arylalkanoic esters via thermal 1,2-rearrangement，Bull chem Soc Jpn,1987, 60:1027~1036
[10] Castadldi G,Cavicchioll S,GiordandI C,et al，Tartaric acid,an efficient chiral auxiliary:new asymmetric synthesis of 2-alkyl-2-aryladtic acids，J. org .Chem,1987, 52:3018~3027
[11] 胡艾希，范国枝，赵海涛.消炎镇痛药萘普生不对称合成，药学学报,1999,34(4):290~292
[12] 刘湘，乔善宝，鲍明伟,等，S-萘普生的不对称合成，无锡轻工大学学报，2000，19（5）:500~502
[13] Tsuchihashi G，Synthesis of optically active 2-arylalkanioc acids by the use
of 1,2-rearrangment of the aryl group，Tetrahedron Lett,1981,22(43):4035~4038
[14] Peri,D, Wyandt, C M, Cleary, R.W, Hikal A H, Jones, A.B. Inclusion complexes of tolnaftate with β-cyclodextrin and hydroxypropyl β-cyclodextrin. Drug. Dev. Ind. Pharm. 1994,20,1401
[15] Kurono Masayasu,Toda Massaak,Nina Haruki,2-(4-Isobutylphenyl)propionic acid,Jp.P, 7753833,1977-04-30
[16] Kaoru Fuji,Manaba Node,Fujie Tanaka,et al,Binaphthol as a Chiral Auxillary Asymmetric Alaylation of Arylaceetic Acid Tetrahedron Lett,1989,30-:2825～2828
[17] Hirooyuki Isshibashi,Momoe Maeki,Junko Yagi,et al，A modification of the asymmetric dihyoxylation approach to the synthesis of (S)-2-arylpropanoic acids ，Tetrahedron,1999,55:6075~6080
[18]Hamon P G,Coghlan D R,Massy-Westropp R A,et al，Asymmetric synthesis of ibuprofen and ketoprofen ，Tetrahedron:Asymmetry, 1993,4(7): 1435~1438
[19] Thayashi ,N Kewamura，Asymmetric hydrogenation of trisubstituted acrylic acies catalyzed by a chiral (aminoalkyl) ferrocenylphosphine-Rhodium acie，J Am Chem Soc,1987,109:7876~7878
[20] 郭荷民，利用不对称交叉偶联反应合成（S）-(+)-萘普生，安徽大学学报（自然科学版），2002,26(2)：77~79
[21] J.D.Morrison,Asymmetric Synthesis(Vol5),New.York:Academic Press ,1985
[22] Dang T P,Kagan H B，Asymmetric synthesis of hydrotropic acid and amino acids by homogeneous catalytic hydyogenation，J .Chem .Soc:ChemCommun,1971,
(10):481~485
[23] Klobucar W.Dirk, Kolich Charles H,Manimanan,et al,Asymmetric hydrogenation of aromatic-substituted olefins using organoruthenium catalysts,U.S.P,5304524,
1994-04-19
[24] Frank R.Fronczek,G.Patrick Stahly,Thanlkavelu Manimaran,In Situ Generation of Ruthenium-Chiral Phosphine Complexes and Their Use in Asymmetric Hydrogenation, Organometalics,1993,12:1467~1470
[25] Pai Cheng Chao,Li Yue Ming ,Zhou Zhong Yuan,et al，Synthesis of new chiral diphosphine ligand (BisbenzodioxanPhos) and its application in asymmetric catalytic hydrogenation，Tetrahedron Lett,2002,43:2789~2792
[26] A Scrivant,U .Matteoli,A Convenient Synthesis of 2-(6-Methoxy-2-naphthyl- -propenoic Acid,Tetrahedron Lett,1995,36(49):9015~9018
[27] Harrison,IanT.,2-(1-Haloethyl)-6-methoxynaphthalenes,U.S.P,3652683, 1972-03-28
[28] Henri Arzoumanian,Gerard Buono,M’Barek Choukrad,et al,Asymmetric Carbonylation of 2-Methylbenzyl Bromide Catalyzed by Oxazaphospholane-Pall-
-adium Complexes under Phase-Transfer Condition,Organometalic,1988,7:59~62
[29] Zhou H Y,Cheng J,Lvsj,Fu H X,Wang H Q，Catalytic Carbonylation of α-(6-methoxyl-2-naphthyl)ethanol to methyl ester of naproxen using PdCl2-CuCl2-PPh3-acid catalyst system ，J Organomet Chem ,1998,556(1):239~242
[30] Eun Duck Park,KYung Hee Lee,Jae Sung Lee，Easily separable molecular catalysis,molecular catalysis:catalysis Today,2000,63：147~157
[31] 李岩云，夏春谷，PVP-PdCl2CuCl2/PPh3体系催化α-（6-甲氧基－2-萘基）乙醇羰化反应研究 ，分子催化，2001，15(2)：129~132
[32] Howard Alper,Nathalie Hamel,Asymmetric Synthesis of Acids by the Palladium-Catalyzed Hydrocarboxylation of Olefins in the Presence of (R)-(-)-or(S)-
(+)-1,1′-Binaphthyl-2,2′-diyl Hydrogen Phosphate,J.Am.Chem.Soc,1990,112:
2083~2084
[33] Baker G.L,Fritschel.S,Stille.K.J,Transition-metal catalyzed asymmetric organic synthesis via polymer-attached optically active phosphine ligand .6.Asymmetric hydrogenation with polymer catalysts containing optically active,pendent alcoh-
-ols,1981,46(14):2960~2965
[34] Rossi R .F, Heefner D. L，Enantioselective production of chiral carboxylic acids,
U.S.P,5 273 895 ,1993－12－28
[35] Garicam ,Delcampo C, Chemoenzymatic synthesis of pure enantiomeric arylpropanic acids ,Tetrahedron,1993,49(37):8433~8440
[36] Thanikavelu Manimaran,Patrick Stahly G,Optical purification of profen drugs,
Tetrahedron:Asymmetry,1993,4(8):1949~1954
[37] Marina Cretich,Marcella Chiari,GlacomoI Carrea,Stereselective synthesis of (S)-(+)-naproxen catalyzed by carboxyl esterase in a multicompartment electrolyzer, J Biochem Biophys Methods,2001,48:247~256
[38] Kenyon.J,Phillips.H,Turley.H.G,Dependence of rotatory power on chiral constitution .XXIV.Futher experiments on the Walden inversion J.Chem.Soc,
1925,127:399~417
[39 ] Tadashi Naka Jima,Yoshiaki Nakamoto,and Sohei Suga,Asymmeric Induction in Friedel-Crafts Reaction with (+)-1,2-Epoxybutane and(-)-2-Chloro--1-butanol, Bull-
-etinof the Chemcial Society of Japan,1975,48(3):960~965
[40] Shoji Kajiaeshi,Hiroshi Kawamukal,Shizuo Fujisaki,Oxidation Using Quaternary Ammonium Polyhalides.Ⅲ.An Effective Oxidation of Alcohols and Ether by the Use of Benzyltrimethylammonium Tribromide,Bull.Chem. Soc.Jpn, 1989,62:
2585~2588
[41] Takashi Morimoto,Masao Hirando,Takayoshi Hamaguchi et al,Oxidation of Alcohols with Peracetic Acid in Ethyl Acetate in the Presence of Sodium Bromide
,Bull Chem. Soc.Jpn,1992,65:703~706
[42] Hiroki Tomioka,Koichiro Oshima,Hitosi Nozaki,Cerium Cataiyzed Selective Oxidation of Secondary Alcohols in the The Presence of Primaryones,Tetrahedron Letters,1982,23(5):539~542
[43] Jean Villieras,Monique Rambaud,Wittig-Horner Reaction in Heterogeneous Media;V1.An Efficient Synthesis of α-Methylenecarboxylic Esters and α-Methyleneketone under Mild Conditions,Synthesis Communications,1984,406~408
[44] Jean Villieras,Monique Rambaud,Wittig-Horner Reaction in Heterogeneous Media;21.A Convenient Synthesis ofα,β-Unsaturated Esters and Kentones using Weak Bases in Water, Synthesis Communications,1983,300~303
[45] M.Finlay*,J.P.Debiard,A.Guy,D.Molko,R.Teoule,An Efficient One-Pot Synthesis of a Fully Protected 2’-Deoxytidine 3’-Monophosphate, Synthesis Communica-
-tions,1983,303~306
[46] N.S.Abramov and Shara Pall,Mechanism of the Arbuzov rearrangement. V.Reaction of ester of bromo substituted carboxylic acids with phosphates,Trudy Kazan. Khim.Tekhnol.Inst.im.S.M.Kirova,1957,23:105~110
[47] J.H.Boyer and D.Straw,Azidocarbonyl compounds.Ⅱ.The pyrolysis of α-azidocarbonyl compounds,J.Am.Chem.Soc,1953,75:1642~1644
[48] Lichty,nitriles of acrylic acids, U.S.P ,2208328,1940-6-16
[49] Joseph Frederic Walker,Westfield,N.J.,Willington,del.,Preparation of Atroponitrile,U.S.P.,2478990,1949-08-16
[50] Brant ,acrylonitriles,U.S.P.,2386586,1945-10-09
[51] Francisco S.Alvarez,Sunnyvale,Calif.,U.S.P.,3637767,1972-01-25
[52] 王清廉，沈凤嘉，有机化学实验（第二版），河北：高等教育出版社，1992.250~254
[53] Chan Albert S.C,Asymmetric catalytic hydrogenation of alpha-arylpropenic
acids ,U.S.P,4994607,1991-02-19
[54] Kunihiko Takabe, Hidetaka Hiyoshi, Hiroyuki Sawada et al. Stereochemistry of thiazolidine ring formation from aminals and cysteine Tetrahedron: Asymmetry, 1992, 3: 1399-1400.
[55]Yasushi Kawai, Motoko Hayashi, Yoshikazu Sawada et al. Asymmetric Reduction of α,β-Unsaturated Ketones with a Carbon-Carbon Double-Bond Reductase from Baker's Yeast Tetrahedron Lett., 1998, 39: 5225-5228
[56] Ezequias P Siqueria Filho, J Augusto R Rodrigues, Paulo J S Moran. Baker's yeast reduction of α-methyleneketones Tetrahedron: Asymmetry, 2001, 12: 847-852
[57] Patrizia Ferraboschi, Shahrzad Beza-Elahi, Elisa Verza et al. Baker's yeast mediated biohydrogenation of unsaturated compounds containing a methylene group: enantioselective preparation of 2-methyl alkanols from 2-substituted acrolein acetals Tetrahedron: Asymmetry, 1999, 10: 2639-2642
[58] Yasushi Kawai, Yoshikazu Inaba, Norihiro Tokitoh. Asymmetric reduction of nitroalke-nes with baker’s yeast Tetrahedron: Asymmetry, 2001, 12: 309-318.
[59] Biswabnath Das, A Kashinatham, P Madhusudhan. Baker’s yeast treatment of some naturally occurring amides Tetrahedron Lett., 1997, 38: 7457-7458
[60] Ahmed Kamal, K Venkata Ramana, Maddamsetty V Rao. Chemoenzymatic synthesis of pyrrolo[2,1-b]quinazolinones: Lipase-Catalyzed resolution of Vasicinone J. Org. Chem., 2001, 66: 997-1001
[61] Fronza G, Fufanti C, Grasselli P et al. Conversion of 4-oxy-substituted crotonaldehyde into 1-protected (2R)-1,2,4-butanetriol: a new synthetic capacity of bakers' yeast J. Org. Chem., 1988, 53: 6153-6154
[62] Fronza G, Fufanti C, Grasselli P et al,on the products obtained from γ-oxygen substituted crotonaldehyde in fermenting baker's yeast, Biocatalysis, 1990, 3: 51-54
[63] 赵桂枝，张卫东，李学良，以酒石酸酯为手性助剂不对称合成萘普生，沈阳医科大学学报，1998，15：193～195
[64] A.S.C.Chan*,T.T.Huang,J.H.Wagenknecht,and R.E.Miller,A Novel Synthesis of 2-ArylacticAcids via Electrocarboxylation of MethylArylKetone,J.org.Chem,1995,60:
742~744
[65] Francisco S.Alvarez,Sunnyvale,,Calif.，2-(6?-Methoxynaphth-2?-yl) Propylene-
-oxide and 5?-Halo Derivatives,U.S.P.,3637767,1972-01-25