Process for preparing optically active allophenylnorstatin derivatives
    21.
    发明授权
    Process for preparing optically active allophenylnorstatin derivatives 失效
    制备光学活性异恶唑诺他抑素衍生物的方法

    公开(公告)号:US5581007A

    公开(公告)日:1996-12-03

    申请号:US609619

    申请日:1996-03-01

    摘要: A process for preparing an optically active (2S,3S)-allophenylnorstatin derivative (I) is disclosed, comprising asymmetrically hydrogenating a 4-phenyl-2-halogeno-3-oxobutyric ester (III) in the presence of a ruthenium-phosphine complex to obtain a 4-phenyl-(2S)-halogeno-(3R)-hydroxybutyric ester (IV), epoxidizing the ester (IV) in the presence of a base to obtain a 4-phenyl-(2S,3R)-epoxybutyric ester (V), reacting the ester (V) with a tri(lower alkyl)silylazide or a (lower alkyl)diarylsilylazide in the presence of a Lewis to obtain a (3S)-azido-4-phenyl-(2S)-trisubstituted silyloxybutyric ester (VI), hydrogenolyzing the ester (VI) into a (2S,3S)-allophenylnorstatin derivative (VII), protecting the amino group of the compound (VII), and, if desired, hydrolyzing the compound before or after the amino group protection. Compounds (I) can be obtained at high optical purity safely and in good yield.

    摘要翻译: 公开了一种制备光学活性(2S,3S) - 萘基异步抑制素衍生物(I)的方法,包括在钌膦络合物存在下不对称氢化4-苯基-2-卤代-3-氧代丁酸酯(III) 得到4-苯基 - (2S) - 卤素 - (3R) - 羟基丁酸酯(IV),在碱的存在下使酯(Ⅳ)环氧化,得到4-苯基 - (2S,3R) - 环氧丁酸酯 V),在路易斯存在下使酯(V)与三(低级烷基)甲硅烷基叠氮化物或(低级烷基)二芳基甲硅烷基叠氮化物反应,得到(3S) - 叠氮基-4-苯基 - (2S) - 三取代的甲硅烷氧基丁酸酯 (Ⅵ),将酯(Ⅵ)氢解成(2S,3S) - 萘基异步抑制素衍生物(Ⅶ),保护化合物(Ⅶ)的氨基,如果需要,在氨基保护之前或之后水解化合物 。 化合物(I)可以安全且高收率地获得高光学纯度。

    Process for preparing optically active 6-t-butyoxy-3,5-dihydroxyhexanoic
esters
    22.
    发明授权
    Process for preparing optically active 6-t-butyoxy-3,5-dihydroxyhexanoic esters 失效
    光学活性6-叔丁氧基-3,5-二羟基己酸酯的制备方法

    公开(公告)号:US4994602A

    公开(公告)日:1991-02-19

    申请号:US485692

    申请日:1990-02-27

    IPC分类号: C07C67/31 C07C69/708

    CPC分类号: C07C67/31 C07C69/708

    摘要: A process for preparing an optically active 6-t-butoxy-3,5-dihydroxyhexanoic ester represented by formula: ##STR1## wherein t-Bu represents a t-butyl group; and R.sup.4 represents a lower alkyl group, which is useful as a precursor of a lactone moiety of campactin, mevinolin or analogues thereof is disclosed, comprising asymmetrically hydrogenating a 4-t-butoxyacetoacetic ester in the presence of a ruthenium-optically active phosphine complex to obtain an optically active 4-t-butyoxy-3-hydroxybutanoic ester, reacting the ester with a lithium enolate of an acetic ester to obtain an optically active 6-t-butyoxy-5-hydroxy-3-oxohexanoic ester, and asymmetrically hydrogenating the resulting ester in the presence of a ruthenium-optically active phosphine complex as a catalyst. The desired product can be obtained in good yield at high stereoselectivity.

    Phosphine compound, complex containing the phosphine compound as ligand,
process for producing optically active aldehyde using the phosphine
compound or the complex, and 4-[(R)-1'-formylethyl]azetidin-2-one
derivatives
    24.
    发明授权
    Phosphine compound, complex containing the phosphine compound as ligand, process for producing optically active aldehyde using the phosphine compound or the complex, and 4-[(R)-1'-formylethyl]azetidin-2-one derivatives 失效
    膦化合物,含膦化合物作为配体的络合物,使用膦化合物或络合物制备旋光醛的方法,以及4 - [(R)-1'-甲酰基乙基]氮杂环丁-2-酮衍生物

    公开(公告)号:US5530150A

    公开(公告)日:1996-06-25

    申请号:US323492

    申请日:1994-10-12

    IPC分类号: C07F9/02 C07F15/00

    CPC分类号: C07F9/02 C07F15/00

    摘要: A phosphine compound represented by one of the formulas: ##STR1## wherein R.sup.1 and R.sup.2, which may be the same or different, each represent a phenyl group or a phenyl group substituted with a halogen atom or a lower alkyl group or taken together form a divalent hydrocarbon group; and R.sup.3 and R.sup.4, which may be the same or different, each represent a lower alkyl group, a phenyl group or a phenyl group substituted with a halogen atom, a lower alkyl group or a lower alkoxy group or taken together form a divalent hydrocarbon group, and wherein R.sup.6 and R.sup.6' which may be the same or different, each represent a hydrogen atom, a lower alkyl group or a lower alkoxy group; R.sup.5, R.sup.5', R.sup.11 and R.sup.11' which may be the same or different, each represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom; or a pair of R.sup.5 and R.sup.6 or a pair of R.sup.5' and R.sup.6' may form a ring; R.sup.7 and R.sup.8, which may be the same or different, each represent a phenyl group or a phenyl group substituted with a lower alkyl group, a halogen atom or a lower alkoxy group; and R.sup.9 and R.sup.10, which may be the same or different, each represent a phenyl group or a phenyl group substituted with a lower alkyl group, a lower alkoxy group or a halogen atom; or R.sup.9 and R.sup.10 may be taken together to form a divalent hydrocarbon group.

    摘要翻译: 由下式之一表示的膦化合物:其中R 1和R 2可以相同或不同,各自表示苯基或苯基(III),其中R 1和R 2可以相同或不同, 被卤素原子或低级烷基取代或一起形成二价烃基; 和可以相同或不同的R 3和R 4各自表示低级烷基,苯基或被卤素原子,低级烷基或低级烷氧基取代的苯基或一起形成二价烃基 并且其中可以相同或不同的R6和R6'各自表示氢原子,低级烷基或低级烷氧基; R5,R5',R11和R11'可以相同或不同,分别表示氢原子,低级烷基,低级烷氧基或卤素原子; 或一对R 5和R 6或一对R 5'和R 6'可以形成环; R 7和R 8可以相同或不同,表示苯基或被低级烷基,卤原子或低级烷氧基取代的苯基; 和R 9和R 10可以相同或不同,各自表示苯基或被低级烷基,低级烷氧基或卤素原子取代的苯基; 或者R 9和R 10可以一起形成二价烃基。

    Ruthenium-phosphine complex
    27.
    发明授权
    Ruthenium-phosphine complex 失效
    钌膦络合物

    公开(公告)号:US4766225A

    公开(公告)日:1988-08-23

    申请号:US130577

    申请日:1987-12-09

    CPC分类号: C07F15/0053 C07C51/36

    摘要: A ruthenium-phosphine complex represented by formula (I): ##STR1## wherein R.sup.1 represents a hydrogen atom, a methyl group, or a methoxy group; and R.sup.2 represents a lower alkyl group, a halogenated lower alkyl group, a phenyl group, or a phenyl group substituted with a lower alkyl group. The complex is inexpensive and exhibits excellent performance as a catalyst for various organic syntheses, particularly for asymmetric hydrogenation.

    摘要翻译: 由式(I)表示的钌膦络合物:其中R 1表示氢原子,甲基或甲氧基; R 2表示低级烷基,卤代低级烷基,苯基或被低级烷基取代的苯基。 该复合物是便宜的,并且作为各种有机合成的催化剂表现出优异的性能,特别是用于不对称氢化。

    Method for producing a ruthenium complex
    29.
    发明授权
    Method for producing a ruthenium complex 有权
    钌络合物的制造方法

    公开(公告)号:US07964744B2

    公开(公告)日:2011-06-21

    申请号:US12540794

    申请日:2009-08-13

    IPC分类号: C07F15/00

    CPC分类号: C07F15/0053

    摘要: Provided is a method for producing a ruthenium complex comprises the step of reacting a ruthenium compound represented by general formula (1): [RuX(L)(PP)]X  (1), wherein Ru represents a ruthenium atom; X represents a halogen atom; L represents an arene; and PP represents an optically active bisphosphine, with a carboxylate salt represented by general formula (2): R1CO2M  (2), wherein M represents a monovalent cation; and R1 represents a group selected from the group consisting of alkyl groups, haloalkyl groups, phenyl groups optionally having a substituent(s), 1-aminoalkyl groups and 1-amino-1-phenylalkyl groups, to produce a ruthenium complex represented by general formula (3): Ru(OCOR1)2(PP)  (3), wherein R1 represents the group selected from the group consisting of alkyl groups, haloalkyl groups, phenyl groups optionally having a substituent(s), 1-aminoalkyl groups and 1-amino-1-phenylalkyl groups; and PP represents the optically active bisphosphine.

    摘要翻译: 提供一种制备钌络合物的方法,包括使通式(1)表示的钌化合物:[RuX(L)(PP)] X(1),其中Ru表示钌原子; X表示卤原子; L代表芳烃; 和PP代表光学活性双膦,与通式(2)表示的羧酸盐:R1CO2M(2),其中M表示一价阳离子; 并且R 1表示选自烷基,卤代烷基,任选具有取代基的苯基,1-氨基烷基和1-氨基-1-苯基烷基的基团,以制备由通式 (3):Ru(OCOR1)2(PP)(3),其中R1表示选自烷基,卤代烷基,任选具有取代基的苯基,1-氨基烷基和1- 氨基-1-苯基烷基; PP代表光学活性双膦。