Catalytic Asymmetric Hydrolysis : Asymmetric Hydrolytic Protonation of Enol Esters Catalyzed by Phase-Transfer Catalysts
Catalytic Asymmetric Hydrolysis : Asymmetric Hydrolytic Protonation of Enol Esters Catalyzed by Phase-Transfer Catalysts
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催化不对称水解：相转移催化剂催化烯醇酯的不对称水解质子化
DOI：
10.1002/chem.201100833
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发表时间：
2011
期刊：
影响因子：
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通讯作者：
et al
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文献类型：
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作者：
E.Yamamoto;et al
除非另有说明，所有的反应都是在火焰干燥的玻璃器皿中使用干燥的溶剂在氮气气氛下进行的。商品试剂按收到的标准使用。在JEOL光谱仪ECS-400、ECS-600和AL-400上记录了~1H和~(13)C核磁共振谱。核磁共振氢谱数据如下：化学位移(δppm)，重数(S=单重态，d=双重态，t=三重态，q=四重态，m=多重态，dd=双重态，AP=表观，性别=六重态，SEp=七重态)，积分，耦合常数(赫兹)和归属。通过使用单个实验中指定的手性固定相柱，通过将样品与适当的外消旋混合物进行比较，通过GC或HPLC分析来确定对映体过量。GC分析采用Agilent GC 6850系列II柱，InertCap CHIRAMIX色谱柱(长度30m，ID 0.25 mm，df)。0.25μm)，来自GL Sciences Inc.和CHIRASIL-DEX CB(长度25 m，ID 0.25 mm，df.0.25μm)来自瓦里安，使用氦作为载气。采用HP-1(长度30m，ID 0.320 mm，df)测定GC产率。μm)或HP-INNOWAX(长度30 m，ID 0.320 mm，df.0.2 5μm)色谱柱，以氦为载气。FAB-MS分析采用材料化学与工程研究所JMS-HX110A超高性能质谱仪。在配备可变波长检测器的JASCO LC-2000 Plus系列色谱柱上，采用Daicel手性固定柱(Chiracel AD-H，0.46 cm x 25 cm)。在JASCO DIP-1000数字旋光仪上测量了旋光度。硅胶(关东化学，硅胶60N，球形，中性；粒度40-100μm)进行层析。缩写：Bn=苄基，转化率=conv，对映体过量=ee，eq=当量，er=对映体比，DMAP=N，N-二甲氨基吡啶，MTPACl=甲氧基-1-(三氟甲基)苯乙酰氯，PIV=甲氧基-1-(三氟甲基)苯乙酰氯，产物=PRO，RT=室温，底物=SUB。
Unless otherwise stated, all the reactions were performed in flame-dried glassware under a nitrogen atmosphere using dry solvents. Commercial reagents were used as received. 1H and 13C NMR spectra were recorded on a JEOL spectrometer ECS-400, ECS-600 and AL-400. Data for 1H NMR spectra are reported as follows: chemical shift (δ ppm), multiplicity (s= singlet, d= doublet, t= triplet, q= quartet, m= multiplet, dd= doublet of doublets, ap= apparent, sex= sextet, sep= septet), integration, coupling constant (Hz) and assignment. The enantiomeric excesses were determined by GC or HPLC analysis employing a chiral stationary phase column specified in the individual experiment, by comparing the samples with the appropriate racemic mixtures. GC analysis was carried out using Agilent GC 6850 series II equipped with InertCap CHIRAMIX Column (length 30 m, iD 0.25 mm, df. 0.25 μm) from GL Sciences Inc. and CHIRASIL-DEX CB (length 25 m, iD 0.25 mm, df. 0.25 μm) from Varian using helium as a carrier gas. GC yields were determined by employing HP-1 (length 30 m, iD 0.320 mm, df. 0.25 μm) or HP-INNOWAX (length 30 m, iD 0.320 mm, df. 0.25 μm) column from Agilent Technologies using helium as a carrier gas. FAB-MS analysis was performed with an Ultrahigh Performance Mass Spectrometer JMS-HX110A in Institute for Materials Chemistry and Engineering (IMCE). HPLC analysis was performed on a JASCO LC-2000 Plus Series equipped with a variable wavelength detector using chiral stationary columns (Chiracel AD-H, 0.46 cm x 25 cm) from Daicel. Optical rotations were measured on a JASCO DIP-1000 digital polarimeter. Chromatography was performed on silica-gel (Kanto Chemicals, Silica gel 60N, spherical, neutral; particle size 40–100 μm). Abbreviations; Bn= benzyl, conversion= conv, enantiomeric excess= ee, eq= equiv, er= enantiomer ratio, DMAP= N, N-dimethylaminopyridine, MTPACl= Methoxy-1-(trifluoromethyl) phenylacetyl chloride, piv= pivaloyl, product= pro, RT= room temperature, substrate= sub.