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    Active catalysts for stereoselective ring-opening reactions
    6.
    发明授权
    Active catalysts for stereoselective ring-opening reactions 失效
    用于立体选择性开环反应的活性催化剂

    公开(公告)号：US06781006B2

    公开(公告)日：2004-08-24

    申请号：US10245110

    申请日：2002-09-17

    申请人： Jay F. Larrow ,  Karl Hemberger ,  Hocine Kabir ,  Philippe Morel

    发明人： Jay F. Larrow ,  Karl Hemberger ,  Hocine Kabir ,  Philippe Morel

    IPC分类号： C07F1100

    CPC分类号： B01J31/2243 ,  B01J37/031 ,  B01J2231/487 ,  B01J2531/0252 ,  B01J2531/62 ,  B01J2531/845 ,  B01J2531/96 ,  C07B53/00 ,  C07F15/065

    摘要： A method for making a chiral transition metal-ligand catalyst complex that is active in catalyzing stereoselective ring opening reactions includes contacting an asymmetric tetradentate ligand, in an excess of a Brønsted acid, with a salt of a first row transition metal, wherein the acidity of the conjugate acid of the salt is the same as or less than the acidity of the Brønsted acid, under conditions effective to allow formation of the active chiral transition metal-ligand catalyst complex, and forming a solution of the complex in a water-miscible, protic solvent from which the active complex can be precipitated by the addition of water and adding water to the solution to precipitate at least a portion of the complex.

    摘要翻译： 制备在催化立体选择性开环反应中有活性的手性过渡金属 - 配体催化剂络合物的方法包括使过量布朗斯台德酸中的不对称四齿配体与第一排过渡金属的盐接触，其中酸 在有效地形成活性手性过渡金属 - 配体催化剂络合物的条件下，该盐的共轭酸与布朗斯台德酸的酸度相同或更小，并且将该络合物的溶液与水混溶， 通过加入水可以使活性络合物沉淀出来，并向溶液中加入水以沉淀至少一部分络合物的质子溶剂。

    Kinetic resolution method
    7.
    发明授权
    Kinetic resolution method 失效
    动力分辨法

    公开(公告)号：US06639087B2

    公开(公告)日：2003-10-28

    申请号：US10225902

    申请日：2002-08-22

    申请人： Jay F. Larrow ,  Serge Jasmin ,  Yi Liu ,  Marcello Di Mare

    发明人： Jay F. Larrow ,  Serge Jasmin ,  Yi Liu ,  Marcello Di Mare

    IPC分类号： C07D30132

    CPC分类号： C07D301/32 ,  C07B2200/07 ,  C07C27/00 ,  C07C29/106 ,  C07C2523/75 ,  C07D303/04 ,  C07D303/08 ,  C07D303/48 ,  Y02P20/584 ,  C07C31/36 ,  C07C31/42 ,  C07C33/26

    摘要： A method for stereoselective chemical synthesis, includes the steps of: (A) reacting a nucleophile and chiral or prochiral cyclic subtrate, said substrate comprising a carbocycle or a heterocycle having a reactive center susceptible to nucleophilic attack by the nucleophile, in the presence of a chiral non-racemic catalyst to produce a product mixture comprising a stereomerically enriched product wherein the product mixture further comprises a catalyst residue, at least a portion of the catalyst residue is in a first oxidation state, and the catalyst residue in the first oxidation state is active in catalyzing degradation of the stereoisomerically enriched product, and (B) chemically or electochemically changing the oxidation state of the catalyst residue from the first oxidation state to a second oxidation state, wherein catalyst residue in the second oxidation state is less active in catalyzing degradation of the stereoisomerically enriched product than is catalyst residue in the first oxidation state. The method reduces erosion of the chiral purity of the stereoisomerically enriched product and reduces the chemical transformation to side products of the stereoisomerically enriched product and co-product(s). The deactivated catalyst is recoverable and recyclable.

    摘要翻译： 一种用于立体选择性化学合成的方法包括以下步骤：（A）使亲核试剂和手性或前手性环状残留物反应，所述底物包含具有易受亲核试剂亲核攻击的反应性中心的碳环或杂环， 手性非外消旋催化剂以产生包含立体富集产物的产物混合物，其中产物混合物还包含催化剂残余物，至少一部分催化剂残余物处于第一氧化态，第一氧化态的催化剂残余物为 有效催化立体异构体富集产物的降解，和（B）将催化剂残余物从第一氧化态的氧化态化学或电化学地改变为第二氧化态，其中在第二氧化态的催化剂残余物在催化降解中的活性较低 的立体异构体富集产物比冷杉中的催化剂残余物 st氧化态。 该方法减少了立体异构体富集产物的手性纯度的侵蚀，并减少了立体异构富集的产物和副产物的副产物的化学转化。 失活的催化剂是可回收和可回收的。