Optically active transition metal-diamine compound and process for producing optically active alcohol with the same
    21.
    发明申请
    Optically active transition metal-diamine compound and process for producing optically active alcohol with the same 有权
    光活性过渡金属 - 二胺化合物及其制备光学活性醇的方法

    公开(公告)号:US20070149831A1

    公开(公告)日:2007-06-28

    申请号:US10594744

    申请日:2005-03-28

    IPC分类号: C07C29/14 C07F15/00

    摘要: The present invention provides a water-soluble transition metal-diamine complex which can be easily separated from reaction products through liquid separation, etc. and is recycleable; an optically active diamine compound constituting the ligand of the complex; and a catalyst for asymmetric synthesis which comprises these. The present invention relates to a water-soluble optically active transition metal-diamine complex represented by the formula (2): [wherein R1 and R2 each represents hydrogen, a hydrocarbon group, —SO2R13 (wherein R13 is a hydrocarbon group, substituted amino, etc.), etc.; R3 to R12 each represents hydrogen, a hydrocarbon group, alkoxy, substituted amino, etc.; M represents a transition metal; X represents halogen; L represents a ligand; and * indicates an asymmetric carbon atom; provided that at least one of R3 to R7 and R8 to R12 is substituted amino], a catalyst for asymmetric synthesis containing the complex, and a process for producing an optically active alcohol, which comprises using the catalyst to asymmetrically reduce a ketone.

    摘要翻译: 本发明提供一种水溶性过渡金属 - 二胺络合物,其可以通过液体分离等容易地从反应产物中分离出来并且是可再循环的; 构成络合物配体的光学活性二胺化合物; 和包含这些的不对称合成催化剂。 本发明涉及由式(2)表示的水溶性光学活性过渡金属 - 二胺络合物:其中R 1和R 2各自表示氢, 烃基,-SO 2 R 13(其中R 13是烃基,取代的氨基等)等; R 12至R 12各自表示氢,烃基,烷氧基,取代的氨基等; M表示过渡金属; X表示卤素; L表示配体; 和*表示不对称碳原子; 条件是R 3至R 7和R 8至R 12中的至少一个为取代的氨基], 含有络合物的不对称合成催化剂,以及制备光学活性醇的方法,其包括使用该催化剂不对称地还原酮。

    Process for preparing ruthenium-phosphine complex
    22.
    发明授权
    Process for preparing ruthenium-phosphine complex 失效
    制备钌膦配合物的方法

    公开(公告)号:US5919962A

    公开(公告)日:1999-07-06

    申请号:US933973

    申请日:1997-09-19

    CPC分类号: C07F15/0053

    摘要: Disclosed is a ruthenium-phosphine complex represented by formula (I):�{RuX(L)}.sub.2 (.mu.-X).sub.3 !.sup.- �R.sub.2 NH.sub.2 !.sup.+(I)wherein R is hydrogen, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted benzyl group; X is halogen; and L is an optically active or inactive tertiary phosphine. A process for preparing the complex (I) is also disclosed, which comprises (A) reacting a ruthenium complex represented by formula: �RuX(arene)(L)!X (wherein arene is a substituted or unsubstituted phenyl group) and an ammonium salt represented by formula (III): R.sub.2 NH.HX, or (B) reacting a ruthenium complex represented by formula: �RuX.sub.2 (arene)!.sub.2, a tertiary phosphine represented by L, and an ammonium salt (III). The complex (I) useful as a catalyst for general syntheses or asymmetric syntheses can be obtained easily in good yield.

    摘要翻译: 公开了由式(I)表示的钌膦配合物:[{RuX(L)} 2(mu -X)3] - [R 2 NH 2] +(I)其中R是氢,具有1至5个碳原子的烷基 原子,环烷基,取代或未取代的苯基或取代或未取代的苄基; X是卤素; L是光学活性或无活性的叔膦。 还公开了制备络合物(I)的方法,其包括(A)使由式[RuX(芳烃)(L)] X(其中芳烃为取代或未取代的苯基)和铵 由式(III)表示的盐:R2NH.HX,或(B)使由式[RuX2(芳烃)] 2表示的钌络合物,由L表示的叔膦和铵盐(III)反应。 可以容易地以良好的收率获得用作一般合成或不对称合成的催化剂的络合物(I)。

    Oxotitanium complex, asymmetric hydrogenation catalyst comprising the
complex, and process for producing .beta.-hydroxy ketone or
.alpha.-hydroxy carboxylic acid ester using the complex
    23.
    发明授权
    Oxotitanium complex, asymmetric hydrogenation catalyst comprising the complex, and process for producing .beta.-hydroxy ketone or .alpha.-hydroxy carboxylic acid ester using the complex 失效
    包含络合物的氧钛复合物,不对称氢化催化剂以及使用络合物生产β-羟基酮或α-羟基羧酸酯的方法

    公开(公告)号:US5714624A

    公开(公告)日:1998-02-03

    申请号:US775205

    申请日:1996-12-30

    摘要: A novel oxotitanium complex represented by general formula (I) is disclosed: ##STR1## wherein R.sup.1 and R.sup.2 may be the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a phenyl group, a substituted phenyl group, a trialkylsilyl group, a monoalkyldiphenylsilyl group, a dialkylmonophenylsilyl group, a triphenylsilyl group, a substituted triphenylsilyl group, or a lower alkoxycarbonyl group, provided that R.sup.1 and R.sup.2 may be bonded to each other to form a hydrocarbon ring or a substituted hydrocarbon ring in cooperation with the carbon atoms to which R.sup.1 and R.sup.2 are bonded; R.sup.3 and R.sup.4 may be the same or different and each represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a benzoyl group, a benzenesulfonyl group, or a halogen atom, provided that R.sup.3 and R.sup.4 may be bonded to each other to form a hydrocarbon ring or a substituted hydrocarbon ring in cooperation with the carbon atoms to which R.sup.3 and R.sup.4 are bonded; and n is 1 or 2. The novel oxotitanium complex is useful as an asymmetric reaction catalyst. A process for producing a .beta.-hydroxy ketone or an .alpha.-hydroxy carboxylic acid ester in the presence of the novel oxotitanium complex is also disclosed.

    摘要翻译: 公开了由通式(I)表示的新型氧代钛络合物:其中R 1和R 2可以相同或不同,各自表示氢原子,低级烷基,低级烷氧基,卤素原子 苯基,取代苯基,三烷基甲硅烷基,单烷基二苯基甲硅烷基,二烷基单苯基甲硅烷基,三苯基甲硅烷基,取代的三苯基甲硅烷基或低级烷氧基羰基,条件是R 1和R 2可以彼此键合形成 与R1和R2键合的碳原子配合的烃环或取代的烃环; R 3和R 4可以相同或不同,并且各自表示氢原子,低级烷基,低级烷氧基,苯甲酰基,苯磺酰基或卤素原子,条件是R 3和R 4可以彼此键合 与R3和R4键合的碳原子一起形成烃环或取代的烃环; 并且n为1或2.新型氧钛复合物可用作不对称反应催化剂。 还公开了在新型氧代钛络合物存在下生产β-羟基酮或α-羟基羧酸酯的方法。

    Process for producing cyclohexylbutyric acid derivative
    25.
    发明授权
    Process for producing cyclohexylbutyric acid derivative 失效
    环己基丁酸衍生物的制备方法

    公开(公告)号:US5442105A

    公开(公告)日:1995-08-15

    申请号:US175505

    申请日:1993-12-30

    摘要: A process for for producing a (2R,3S)-cyclohexylnorstatine or a salt thereof is disclosed, which comprises the steps of: enantioselectively hydrogenating a 4-cyclohexyl-2-halogeno-3-oxobutyric acid ester in the presence of a ruthenium-phosphine complex to produce a 4-cyclohexyl-2-halogeno-(3R)-hydroxybutyric acid ester (2); epoxidizing the compound (2) in the presence of a base to produce a 4-cyclohexyl-(2S,3R)-epoxybutyric acid ester (3); reacting the compound (3) with a lower trialkylsilyl azide in the presence of a Lewis acid to produce a (3S)-azide-4-cyclohexyl-(2S)-substituted butyric acid ester (4); subjecting the compound (4) to hydrogenolysis to produce a (2S,3S)-cyclohexylnorstatine derivative (5); and inverting the configuration at the 2-position of the compound (5).

    摘要翻译: 公开了一种制备(2R,3S) - 环己基异腈或其盐的方法,其包括以下步骤:在钌 - 磷化氢存在下对4-选择性氢化4-环己基-2-卤代-3-氧代丁酸酯 复合以制备4-环己基-2-卤代 - (3R) - 羟基丁酸酯(2); 在碱的存在下使化合物(2)环氧化,得到4-环己基 - (2S,3R) - 环氧丁酸酯(3); 在路易斯酸存在下使化合物(3)与低级三烷基甲硅烷基叠氮化物反应,得到(3S) - 叠氮-4-环己基 - (2S) - 取代的丁酸酯(4); 使化合物(4)进行氢解以制备(2S,3S) - 环己基稳定剂衍生物(5); 并使化合物(5)的2位的构型反转。

    Process for producing optically active dihydropyran derivative
    27.
    发明授权
    Process for producing optically active dihydropyran derivative 失效
    光学活性二氢吡喃衍生物的制备方法

    公开(公告)号:US5155240A

    公开(公告)日:1992-10-13

    申请号:US668656

    申请日:1991-03-13

    IPC分类号: C07D309/28

    CPC分类号: C07D309/28

    摘要: A process for producing an optically active dihydropyran derivative represented by formula (1): ##STR1## wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 each represents a hydrogen atom, a lower alkyl group, a tri-lower alkylsilylmethyl group, a lower alkoxycarbonylamino group, or an --OR.sup.5 group, wherein R.sup.5 represents a lower alkyl group, a lower acyl group, a lower alkoxycarbonyl group, a di-lower alkylcarbamoyl group, or a tri-lower alkylsilyl group, or R.sup.1 and R.sup.2 are taken together to form a 5- to 7-membered cyclic hydrocarbon group or to form a condensed heterocyclic group with an oxygen atom, or R.sup.2 and R.sup.3 are taken together to form a 5- to 7-membered cyclic hydrocarbon group or to form a condensed heterocyclic group with an oxygen atom, provided that all of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 do not represent hydrogen atoms at the same time; and R.sup.6 represents a lower alkyl group, which comprises reacting a diene compound represented by formula (2): ##STR2## wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 have the same meanings as defined above, with a glyoxylic acid ester represented by formula (3): ##STR3## wherein R.sup.6 has the same meaning as defined above, in the presence of a binaphthol-titanium complex represented by formula (4): ##STR4## wherein X represents a chlorine atom or a bromine atom, is disclosed.

    摘要翻译: 一种制备式(1)表示的光学活性二氢吡喃衍生物的方法:其中R1,R2,R3和R4各自表示氢原子,低级烷基,三低级烷基甲硅烷基甲基, 低级烷氧基羰基氨基或-OR5基团,其中R5表示低级烷基,低级酰基,低级烷氧基羰基,二低级烷基氨基甲酰基或三低级烷基甲硅烷基,或者R1和R2组合在一起 形成5至7元环状烃基或与氧原子形成稠合杂环基,或将R 2和R 3一起形成5-至7-元环状烃基或形成稠合杂环基 具有氧原子,条件是所有R1,R2,R3和R4不同时表示氢原子; 并且R 6表示低级烷基,其包括使式(2)表示的二烯化合物:其中R 1,R 2,R 3和R 4具有与上述相同的含义,与表示的二羟乙酸酯反应 在式(4)表示的联萘酚钛化合物存在下,式(3)表示:其中R 6具有与上述相同的含义,其中X表示氯原子 或溴原子。

    METHOD FOR PRODUCING A RUTHENIUM COMPLEX
    30.
    发明申请
    METHOD FOR PRODUCING A RUTHENIUM COMPLEX 有权
    生产金属复合材料的方法

    公开(公告)号:US20100076210A1

    公开(公告)日:2010-03-25

    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。