Iridium-optically active phosphine complex and process for producing
optically active alcohols using the same
    63.
    发明授权
    Iridium-optically active phosphine complex and process for producing optically active alcohols using the same 失效
    铱 - 光学活性膦配合物和使用其制备光学活性醇的方法

    公开(公告)号:US5210332A

    公开(公告)日:1993-05-11

    申请号:US856403

    申请日:1992-03-20

    IPC分类号: C07F15/00

    CPC分类号: C07F15/004

    摘要: An iridium-optically active phosphine complex represented by formula (I):[H.sub.2 Ir(L.sup.1)(L.sup.2)]Y (I)wherein L.sup.1 represents an optically active phosphine compound represented by formula (II): ##STR1## wherein Ar represents a phenyl group or a p- and/or m-lower alkyl-substituted phenyl group, or formula (III): ##STR2## L.sup.2 represents a tertiary phosphine compound represented by formula (IV): ##STR3## wherein Z represents a lower alkoxy group or a di-lower alkylamino group; and A represents an integer of from 1 to 3; Y represents BF.sub.4, PF.sub.6, ClO.sub.4, or BPh.sub.4, wherein Ph represents a phenyl group,and a process for producing an optically active alcohol using the above complex as an enantioselective catalyst are disclosed. The complex exhibits excellent catalytic activity to give high enantioselective yields in enantioselective synthesis, particularly enantioselective hydrogenation.

    摘要翻译: 由式(I)表示的铱光学活性膦配合物:[H2Ir(L1)(L2)] Y(I)其中L1表示由式(II)表示的光学活性膦化合物:其中Ar (III)表示式(IV)表示的叔膦化合物:(IV)表示的叔膦化合物:其中, )其中Z表示低级烷氧基或二低级烷基氨基; A表示1〜3的整数, Y表示BF4,PF6,ClO4或BPh4,其中Ph表示苯基,并且公开了使用上述络合物作为对映选择性催化剂制备光学活性醇的方法。 复合物显示出优异的催化活性,以在对映选择性合成,特别是对映选择性氢化中提供高对映选择性的产率。

    Process for production of optically active
2-(tetrahydropyran-2-yloxy)-1-propanol
    64.
    发明授权
    Process for production of optically active 2-(tetrahydropyran-2-yloxy)-1-propanol 失效
    生产光学活性2-(四氢吡喃-2-基)-1-丙醇的方法

    公开(公告)号:US5128489A

    公开(公告)日:1992-07-07

    申请号:US592752

    申请日:1990-10-04

    IPC分类号: C07D309/12 C07D498/06

    CPC分类号: C07D309/12

    摘要: A process for production of an optically active isomer of 2-(tetrahydropyran-2-yloxy)-1-propanol represented by formula (I): ##STR1## is disclosed, which comprises reacting an optically active isomer of a 1-acyloxy-2-propanol represented by formula (II): ##STR2## wherein R is a substituted or unsubstituted aryl group, with 3,4-dihydro-2H-pyran to obtain an optically active isomer of a 1-acyloxy-2-(tetrahydropyran-2-yloxy)propane represented by formula (III): ##STR3## wherein R is as defined above, and hydrolyzing the compound (III) to eliminate the acyl group. The optically active isomer of 2-(tetrahydropyran-2-yloxy)-1-propanol represented by formula (I) is an intermediate for synthesis of pyridobenzoxazine derivatives useful as a synthetic antibacterial agent, particularly an optically active isomer of ofloxacin.

    Process for preparing optically active threonine
    65.
    发明授权
    Process for preparing optically active threonine 失效
    光学活性苏氨酸制备方法

    公开(公告)号:US4906773A

    公开(公告)日:1990-03-06

    申请号:US287434

    申请日:1988-12-21

    摘要: A process for preparing optically active threonine is disclosed, which comprises asymmetrically hydrogenating a 2-N-acylaminoacetoacetic ester represented by formula (I): ##STR1## wherein R.sup.1 represents a lower alkyl group, a phenyl group, a phenyl group substituted with a lower alkyl group or a lower alkoxy group, a benzyl group, or a benzyl group substituted with a lower alkyl group or a lower alkoxy group; R.sup.2 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a phenyl group substituted with a lower alkyl group or a lower alkoxy group, a benzyloxy group, or a benzyloxy group substituted with a lower alkyl group or a lower alkoxy group, in the presence of a ruthenium-optically active phosphine complex as a catalyst to obtain an optically active threonine derivative represented by formula (II): ##STR2## wherein R.sup.1 and R.sup.2 are as defined above, and then hydrolyzing the compound of formula (II). The 2-N-acylaminoacetoacetic ester intermediate can be selectively prepared in a high yield. Either natural type threonine or non-natural type threonine can be prepared selectively by selecting the absolute configuration of the ligand of the ruthenium-optically active phosphine complex.

    Process for preparing N-acyltetrahydroisoquinoline
    66.
    发明授权
    Process for preparing N-acyltetrahydroisoquinoline 失效
    制备N-酰基四氢异喹啉的方法

    公开(公告)号:US4851537A

    公开(公告)日:1989-07-25

    申请号:US38571

    申请日:1987-04-15

    CPC分类号: C07D217/06 C07D217/20

    摘要: A process for preparing an N-acyltetrahydroisoquinoline represented by formula (II) ##STR1## wherein A represents a phenylene ring substituted with a hydroxyl group, a lower alkoxy group, an acetoxy group, or a benzyloxy group; R represents a hydrogen atom, a lower alkyl group, or a phenyl group; and X represents a hydrogen atoms, a phenyl group, or a phenyl group substituted with a hydroxyl group, a lower alkoxy group, or an acetoxy group, which comprises asymmetrically hydrogenating an N-acyl-1-methylenetetrahydroisoquinoline or N-acyl-1-benzylidenetetrahydroisoquinoline represented by formula (I) ##STR2## wherein A, R, and X are as defined above, in the presence of an optically active ruthenium-phosphine complex as a catalyst. The process exclusively and efficiently provides a useful isomer of the N-acyltetrahydroisoquinoline of high purity which is useful as an intermediate for synthesizing isoquinoline type alkaloids as pharmaceuticals without involving optical resolution of a racemate.

    摘要翻译: 制备由式(II)表示的N-酰基四氢异喹啉的方法其中A表示被羟基,低级烷氧基,乙酰氧基或苄氧基取代的亚苯基环; R表示氢原子,低级烷基或苯基; X表示氢原子,苯基或被羟基,低级烷氧基或乙酰氧基取代的苯基,其包括不对称地氢化N-酰基-1-亚甲基四氢异喹啉或N-酰基-1- 由式(I)表示的亚苄基四氢异喹啉,其中A,R和X如上所定义,在光学活性钌 - 膦配合物作为催化剂存在下进行。 该方法专门有效地提供了高纯度的N-酰基四氢异喹啉的有用异构体,其可用作合成异喹啉类生物碱作为药物而不涉及外消旋物的光学拆分的中间体。

    Rhodium-phosphine complex
    68.
    发明授权
    Rhodium-phosphine complex 失效
    铑膦络合物

    公开(公告)号:US4604474A

    公开(公告)日:1986-08-05

    申请号:US714281

    申请日:1985-03-21

    摘要: A novel rhodium-phosphine complex represented by the formula[Rh(p-Tolyl BINAP).sub.2 ].sup.+ Y.sup.-wherein p-Tolyl BINAP represents 2,2'-bis(di-p-tolylphosphino)-1,1'-binaphthyl, and Y represents ClO.sub.4, PF.sub.6, BF.sub.4 or PCl.sub.6 is described. This complex can be used as a catalyst for various organic syntheses and also for asymmetric syntheses such as an asymmetric isomerization reaction and an asymmetric hydrogenation reaction. Due to its high activity, the complex is very useful as a catalyst.

    摘要翻译: 由式[Rh(对甲苯基BINAP)2] + Y-表示的新型铑 - 膦配合物,其中对甲苯基BINAP表示2,2'-双(二对甲苯基膦基)-1,1'-联萘, 并描述Y表示ClO 4,PF 6,BF 4或PCl 6。 该络合物可用作各种有机合成的催化剂,也可用作不对称异构化反应和不对称氢化反应的不对称合成。 由于其活性高,络合物作为催化剂是非常有用的。