Synthesis of aryl serines
    7.
    发明授权
    Synthesis of aryl serines 失效
    芳基丝氨酸的合成

    公开(公告)号:US6057473A

    公开(公告)日:2000-05-02

    申请号:US50222

    申请日:1998-03-26

    摘要: Anthraquinone chiral ligands (AQN) are used in asymmetric aminohydroxylation addition reactions of cinnamate based olefins for synthesizing aryl serines. The anthraquinones impart a reverse regioselectivity as compared to the commonly employed phalazine chiral ligands (PHAL). Carbamates are employed as the oxidant nitrogen source. The yields and enantiomeric efficiencies are Excellent. .beta.-Hydroxyamines are obtained by deprotecting the corresponding .beta.-hydroxycarbamate.

    摘要翻译: 蒽醌手性配体(AQN)用于肉桂酸酯类烯烃合成芳基丝氨酸的不对称氨基羟基化反应。 与常用的哒嗪手性配体(PHAL)相比,蒽醌赋予反向区域选择性。 使用氨基甲酸酯作为氧化剂氮源。 产率和对映体效率优异。 通过脱保护相应的β-羟基氨基甲酸酯获得β-羟基胺。

    Optically active enantiomers of substituted glyceraldehydes or
glycidaldehydes formed as subtituted 1,5- dihydro-3H-2,4-benzodioxepines
    9.
    发明授权
    Optically active enantiomers of substituted glyceraldehydes or glycidaldehydes formed as subtituted 1,5- dihydro-3H-2,4-benzodioxepines 失效
    由取代的1,5-二氢-3H-2,4-苯并二氧杂环庚三烯形成的取代的甘油醛或缩水甘醛的光学活性对映异构体

    公开(公告)号:US5162554A

    公开(公告)日:1992-11-10

    申请号:US716902

    申请日:1991-06-18

    摘要: Stable, optically active enantiomers of substituted glyceraldehydes or glycidaldehydes are synthesized by using osmium-catalyzed asymmetric dihydroxylation of an olefin which is a substituted 1,5-dihydro-3H-2,4-benzodioxepine. For example, the protected glyceraldehyde, 3-(1,2-dihydroxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine and the protected glycidaldehyde, 3-(1,2-epoxyethyl)-1,5-dihydro-3H-2,4-benzodioxepine have been synthesized and the optical enantiomer has been recovered. In the synthetic and isolation methods, enantiomers with high enantiomeric excess are recovered from the mother liquor following a recrystallization step.

    摘要翻译: 通过使用锇催化的不对称二羟基化的烯烃(其是取代的1,5-二氢-3H-2,4-benzodioxepine)来合成取代的甘油醛或缩水甘醛的稳定的旋光活性对映异构体。 例如,保护的甘油醛,3-(1,2-二羟乙基)-1,5-二氢-3H-2,4-苯并二氧杂环庚烯和被保护的缩二醛,3-(1,2-环氧乙基)-1,5-二氢 -3H-2,4-苯并二氧杂环庚烯,并回收了光学对映体。 在合成和分离方法中,在重结晶步骤后从母液中回收具有高对映体过量的对映异构体。

    Epoxidation of olefins
    10.
    发明授权

    公开(公告)号:US06271400B1

    公开(公告)日:2001-08-07

    申请号:US09177393

    申请日:1998-10-23

    IPC分类号: C07D30103

    摘要: An process for epoxidizing diversely functionalized olefins by oxorhenium catalysis employs conditions which control water concentration. By controlling water concentration, one can maximize monoperoxo complex formation and increase turnover which subsequently reduces diol side products obtained from epoxide ring opening and increases the yield of the desired epoxide product. The optimal range of water concentrations is 0.50-80.0 mol %. Using less than 0.5 mol % water does not result in practical turnovers and 1.0 equivalent of water (or more) is detrimental to the lifetime of the active catalytic species formed. More particularly, there are four aspects to controlling water concentration: 1) anhydrous oxidants using trialkylsilyl peroxides and an in situ source of BTSP eliminating the need for its isolation; 2) water removal agents including molecular sieves (Aldrich, 3 Å, 4 Å) and common inorganic dehydrating agents; 3) rhenium catalysts; and 4) a boiling reactor process in the context of oxorhenium catalyzed epoxidation.