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    Combination approach to chiral reagents or catalysts having amine or amino alcohol ligands
    4.
    发明授权
    Combination approach to chiral reagents or catalysts having amine or amino alcohol ligands 有权
    具有胺或氨基醇配体的手性试剂或催化剂的组合方法

    公开(公告)号：US06602817B1

    公开(公告)日：2003-08-05

    申请号：US09425498

    申请日：1999-10-22

    申请人： Nicos A. Petasis

    发明人： Nicos A. Petasis

    IPC分类号： B01J3100

    CPC分类号： B01J31/2243 ,  B01J31/1805 ,  B01J31/223 ,  B01J2219/00738 ,  B01J2219/00745 ,  B01J2219/00747 ,  B01J2531/10 ,  B01J2531/20 ,  B01J2531/30 ,  B01J2531/40 ,  B01J2531/82 ,  B01J2531/84 ,  C07B53/00 ,  C07B2200/07 ,  C07C215/28 ,  C07C215/30 ,  C07C215/50 ,  C07C229/36 ,  C07D307/52 ,  C07K5/06026 ,  C40B30/08 ,  C40B40/18

    摘要： Functionalized amine derivatives are prepared by reacting an amine, a carbonyl derivative, and an organoboron compound under mild conditions. Organoboronic acids react with amines and alpha-hydroxy aldehydes to give anti-alpha-amino alcohols with very high diastereoselectivities (>99% de). When optically pure alpha-hydroxy aldehydes are used in this process, no racemization occurs and the products are obtained with very high enantioselectivities (>99% ee). The reaction also works with unprotected glyceraldehyde to give the corresponding amino diol derivatives, while unprotected carbohydrates give the corresponding amino polyols. The chiral amino alcohol products of this process or their derivatives, react further with metals or non-metals to give adducts that are effective catalysts for a variety of asymmetric reactions. Overall, the present invention relies on the facile synthesis of the chiral amino alcohol ligands for the rapid construction of combinatorial libraries of chiral catalysts. These libraries can then be used to identify the most suitable catalyst for a particular asymmetric transformation.

    摘要翻译： 官能化胺衍生物通过在温和条件下使胺，羰基衍生物和有机硼化合物反应来制备。 有机硼酸与胺和α-羟基醛反应得到具有非常高的非对映选择性（> 99％de）的抗α-氨基醇。 当在该方法中使用光学纯的α-羟基醛时，不会发生外消旋化，并且以非常高的对映选择性（> 99％ee）获得产物。 该反应也适用于未保护的甘油醛，得到相应的氨基二醇衍生物，而未保护的碳水化合物则得到相应的氨基多元醇。 该方法的手性氨基醇产物或其衍生物进一步与金属或非金属反应，得到作为各种不对称反应的有效催化剂的加合物。 总之，本发明依赖于手性氨基醇配体的容易合成，用于快速构建手性催化剂组合文库。 然后可以使用这些文库来识别用于特定不对称转化的最合适的催化剂。

    Metal complex catalysts
    6.
    发明授权
    Metal complex catalysts 失效
    金属络合催化剂

    公开(公告)号：US4279829A

    公开(公告)日：1981-07-21

    申请号：US090161

    申请日：1979-10-31

    申请人： Louis J. Velenyi ,  Christos Paparizos ,  Serge R. Dolhyj

    发明人： Louis J. Velenyi ,  Christos Paparizos ,  Serge R. Dolhyj

    IPC分类号： B01J31/22 ,  C07C37/08 ,  C07F3/06

    CPC分类号： C07C37/08 ,  B01J31/226 ,  B01J2531/10 ,  B01J2531/20 ,  B01J2531/26 ,  B01J2531/80 ,  B01J2531/847 ,  Y02P20/52

    摘要： Hydroperoxides are catalytically decomposed using a novel metal complex of the formula: ##STR1## wherein M is a positively charged metal or metal compound;Z is S, O, P, S--P, or S--S;L is C, P, or N; andA is selected from the group consisting of halogens; hydrogen; N--R wherein R is selected from the group consisting of H, C.sub.1-30 alkyls and 4 to 8 membered aryls optionally substituted with one or more C.sub.1-20 alkyls and C.sub.1-20 alkoxys; and hydrocarbon groups containing up to 30 carbon atoms optionally substituted with halogen atoms, C.sub.1-12 hydroxy groups, C.sub.1-12 acid groups, C.sub.1-12 aldehyde groups, C.sub.1-12 ketone groups, and C.sub.1-10 nitrile groups; andwhereinn is 1 or 2; andb is 1, 2 or 3.These catalysts are especially effective in decomposing either cumene hydroperoxide or cyclohexylbenzene hydroperoxide to phenol.

    摘要翻译： 氢过氧化物使用下式的新型金属络合物催化分解：其中M是带正电荷的金属或金属化合物; Z是S，O，P，S-P或S-S; L是C，P或N; 并且A选自卤素; 氢; N-R其中R选自H，C 1-30烷基和任选被一个或多个C 1-20烷基和C 1-20烷氧基取代的4至8元芳基; 含有至多30个碳原子的烃基，任选被卤素原子取代，C 1-12羟基，C 1-12酸基，C 1-12醛基，C 1-12酮基和C 1-10腈基; 并且其中n为1或2; 和b是1,2或3.这些催化剂在将氢过氧化枯烯或环己基苯氢过氧化物分解成酚时特别有效。

    Carbonylation process
    7.
    发明授权
    Carbonylation process 失效
    羰基化过程

    公开(公告)号：US4250329A

    公开(公告)日：1981-02-10

    申请号：US42425

    申请日：1979-05-25

    申请人： Gary B. McVicker

    发明人： Gary B. McVicker

    IPC分类号： B01J31/20 ,  B01J31/24 ,  C07C2/46 ,  C07C45/50 ,  C07C67/36

    CPC分类号： B01J31/1805 ,  B01J31/0231 ,  B01J31/18 ,  B01J31/181 ,  B01J31/20 ,  B01J31/2226 ,  B01J31/2295 ,  B01J31/24 ,  C07C2/465 ,  C07C45/50 ,  C07C67/36 ,  B01J2231/34 ,  B01J2531/0205 ,  B01J2531/20 ,  B01J2531/22 ,  B01J2531/80 ,  B01J2531/845

    摘要： A carbonylation process for the preparation of carboxylic acid esters is described wherein carbon monoxide is contacted with at least one alcohol in the presence of a catalyst system having the general formula:B.sub.x Me[Me'(CO).sub.a (L).sub.b ].sub.2and a cocatalyst comprising halogen containing compounds in a cocatalyst to catalyst molar ratio ranging from about 1 to about 16, wherein B is a Lewis base capable of coordinating with a Group IIA metal; Me is a Group IIA metal, preferably magnesium, Me' is a transition metal selected from the group consisting of metals of Groups VIB, VIIB and VIII of the Periodic Table of the Elements; L is a uni- or polydentate ligand or hydrocarbon capable of coordinating with the transition metal; x is a positive integer ranging from 1 to 4; a is a positive integer ranging from 1 to 5 and b is an integer ranging from 0 to 4, with the proviso that the sum of a and b is 5 or less. A typical preferred catalyst system is represented by the general formula: (C.sub.4 H.sub.8 O).sub.4 Mg[Co(CO).sub.3 P(C.sub.4 H.sub.9).sub.3 ].sub.2 and a cocatalyst comprising methyl iodide.

    摘要翻译： 描述了用于制备羧酸酯的羰基化方法，其中一氧化碳在具有以下通式的催化剂体系存在下与至少一种醇接触：BxMe [Me'（CO）a（L）b] 2和 助催化剂包括助催化剂中的含卤素化合物与催化剂摩尔比为约1至约16，其中B为能与IIA族金属配位的路易斯碱; Me是IIA族金属，优选镁，Me'是选自元素周期表的VIB族，VIIB族和VIII族的金属的过渡金属; L是能够与过渡金属配位的单齿或多齿配体或烃; x是从1到4的正整数; a为1〜5的整数，b为0〜4的整数，条件是a和b的和为5以下。 典型的优选催化剂体系由以下通式表示：（C 4 H 8 O）4 Mg [Co（CO）3 P（C 4 H 9）3] 2和包含甲基碘的助催化剂。