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37 条记录 (耗时 0.029 秒)

    Epoxidation of olefins
    1.
    发明授权
    Epoxidation of olefins 有权

    公开(公告)号：US06271400B1

    公开(公告)日：2001-08-07

    申请号：US09177393

    申请日：1998-10-23

    申请人： K. Barry Sharpless ,  Andrei K. Yudin

    发明人： K. Barry Sharpless ,  Andrei K. Yudin

    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.

    Synthesis of aryl serines
    5.
    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

    申请人： K. Barry Sharpless ,  Beata Tao ,  Gunther Schlingloff

    发明人： K. Barry Sharpless ,  Beata Tao ,  Gunther Schlingloff

    IPC分类号： C07C227/20 ,  C07C229/34 ,  C07C269/00 ,  C07F9/40 ,  C07C229/28

    CPC分类号： C07F9/4056 ,  C07C227/20 ,  C07C269/00 ,  C07F9/4006 ,  C07C2102/10

    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
    7.
    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

    申请人： K. Barry Sharpless ,  Ryu Oi

    发明人： K. Barry Sharpless ,  Ryu Oi

    IPC分类号： C07D321/10 ,  C07D407/04 ,  C07D411/04

    CPC分类号： C07D407/04 ,  C07D321/10 ,  C07D411/04

    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。

    Accelerated catalysis of olefinic epoxidations
    9.
    发明授权
    Accelerated catalysis of olefinic epoxidations 失效
    烯烃环氧化物的加速催化

    公开(公告)号：US5939568A

    公开(公告)日：1999-08-17

    申请号：US842732

    申请日：1997-04-16

    申请人： K. Barry Sharpless ,  Joachim Rudolph

    发明人： K. Barry Sharpless ,  Joachim Rudolph

    IPC分类号： C07D301/12 ,  C07D303/00

    CPC分类号： C07D301/12

    摘要： Rhenium-catalyzed epoxidation of olefinic substrates is accelerated by the use of acclerants having a nitrogenous aromatic heterocyclic structure. Use of the accelerants also enables the use of aqueous hydrogen peroxide as an oxidant. To achieve optimum acceleration, the accelerant should have a concentration within a range from 2.0 mole percent to 100 mole percent of the acclerant with respect to 1 mole of the olefinic substrate. Use of the accelerant also results in an increased yield with respect to the conversion of the olefinic substrate to epoxide product.

    摘要翻译： 通过使用具有含氮芳族杂环结构的增加剂来加速烯属底物的铼催化环氧化。 使用促进剂也可以使用过氧化氢水溶液作为氧化剂。 为了达到最佳加速，促进剂的浓度应在1摩尔烯属底物的2.0摩尔％至100摩尔百分数之间。 促进剂的使用也导致相对于烯属底物转化为环氧化物产物的增加的产率。

    Catalytic asymmetric aminohydroxylation of olefins with carbamates
    10.
    发明授权
    Catalytic asymmetric aminohydroxylation of olefins with carbamates 失效
    烯烃与氨基甲酸酯的催化不对称氨基羟基化

    公开(公告)号：US5767304A

    公开(公告)日：1998-06-16

    申请号：US651104

    申请日：1996-05-21

    申请人： K. Barry Sharpless ,  Guigen Li

    发明人： K. Barry Sharpless ,  Guigen Li

    IPC分类号： C07C227/20 ,  C07C229/34 ,  C07C269/00 ,  C07F9/40 ,  C07C271/16

    CPC分类号： C07F9/4056 ,  C07C227/20 ,  C07C269/00 ,  C07F9/4006 ,  C07C2102/10

    摘要： .beta.-Hydroxyamines and .beta.-hydroxycarbamates are synthesized from olefin substrates by means on a catalyzed asymmetric addition reaction. The addition reaction is catalyzed by osmium and is co-catalyzed by chiral ligands. The chiral ligands, in addition to being co-catalysts with the osmium, also serve to direct the addition reaction regioselectively and enantioselectively. Divalent ligands are preferred over monovalent ligands because of their enhance regio- and enantio-selectivity. Carbamates are employed as an oxidant nitrogen source for the production of .beta.-hydroxysulfonamides. Excellent yields and enantiomeric efficiencies are achieved with co-solvents containing a 50/50 (v/v) mixtures of water and organic solvent. The performance of the reaction is further enhanced by omitting the addition silver or mercurial salts conventionally employed in asymmetric aminohydroxylation additions to olefins performed in neat or substantially neat solvents. .beta.-Hydroxyamines are then obtained by deprotecting the corresponding .beta.-hydroxycarbamate.

    摘要翻译： 通过催化不对称加成反应，通过烯烃底物合成β-羟基胺和β-羟基氨基甲酸酯。 加成反应由锇催化并被手性配体共催化。 除了与锇共助催化剂之外，手性配体还用于区域选择地和对映选择性地引导加成反应。 二价配体优于一价配体，因为它们具有增强的区域和对映选择性。 使用氨基甲酸酯作为生产β-羟基磺酰胺的氧化剂氮源。 使用含有水和有机溶剂的50/50（v / v）混合物的共溶剂可获得优异的收率和对映体效率。 通过省略常规用于在纯净或基本上纯的溶剂中进行的烯烃的不对称氨基羟基化添加中的加成银或汞盐进一步提高反应的性能。 然后通过脱保护相应的β-羟基氨基甲酸酯得到β-羟基胺。