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    • 1. 发明授权
    • Optically active phosphorous compounds
    • 光活性磷化合物
    • US5516944A
    • 1996-05-14
    • US315791
    • 1994-09-30
    • Emil A. BrogerMarco CereghettiAlain Rageot
    • Emil A. BrogerMarco CereghettiAlain Rageot
    • C07C67/31C07F9/50C07F9/6568C07F15/00C07F9/02
    • C07F15/0053C07C67/31C07F9/5027C07F9/65683
    • The present invention is concerned with novel optically active phosphorus compounds of the general formula ##STR1## wherein R and R.sup.1 each independently signify hydroxy, a protected hydroxy group, lower alkyl or lower alkoxy andR.sup.2 to R.sup.5 each independently signify alkyl with 3 to 7 carbon atoms, cycloalkyl or aryl or R.sup.2 and R.sup.3 or R.sup.4 and R.sup.5 together with the phosphorus form a group of the formula ##STR2## wherein R2 and R3 are different when R4 and R5 are the same, and R4 and R5 are different when R2 and R3 are the same,the manufacture of such compounds, their use for enantioselective reactions, such as, e.g., asymmetric hydrogenations, enantioselective hydrogen displacements in prochiral allylic systems and the like, as well as complexes of the compounds of formula I with Group VIII metals.
    • 本发明涉及通式为“IMAGE”I的新型光学活性磷化合物,其中R和R 1各自独立地表示羟基,保护的羟基,低级烷基或低级烷氧基,R2至R5各自独立地表示具有3至7个的烷基 碳原子,环烷基或芳基或R2和R3或R4和R5与磷一起形成下式的基团:其中当R 4和R 5相同时,R 2和R 3不同,R 4和R 5在R 2和 R3相同,制备这些化合物,它们用于对映选择性反应,例如不对称氢化,前手性烯丙基体系中的对映选择性氢置换等,以及式I化合物与VIII族金属的络合物 。
    • 4. 发明授权
    • Chiral rhodium-diphosphine complexes
    • 手性铑 - 二膦配合物
    • US5142063A
    • 1992-08-25
    • US616160
    • 1990-11-20
    • Emil A. BrogerYvo Crameri
    • Emil A. BrogerYvo Crameri
    • B01J31/24C07B35/02C07B53/00C07B61/00C07C55/10C07C59/08C07D307/32C07D307/33C07F15/00
    • B01J31/223B01J31/189B01J31/2291B01J31/2295B01J31/2414B01J31/2495C07D307/33C07F15/008B01J2231/643B01J2231/645B01J2531/822B01J2540/10B01J2540/20B01J2540/22B01J2540/225B01J31/1805B01J31/1875
    • The present invention describes novel chiral rhodium-diphosphine complexes having the formula[Rh(X) (Y) (Lp)]owherein X represents a residue of the formula X--COO.sup.- in which Z signifies a group ##STR1## aryl or substituted aryl, wherein R.sup.1, R.sup.2, R.sup.3 =hydrogen, halogen, lower alkyl, aryl-lower alkyl, perfluoro-C.sub.1-20 -alkyl, aryl, substituted aryl, the group --OR.sup.7, --(CH.sub.2).sub.m --COA or AOC--(CF.sub.2).sub.n, with the proviso that at least one of R.sup.1, R.sup.2, and R.sup.3 represents --OR.sup.7, aryl or substituted aryl,R.sup.4, R.sup.5, R.sup.6 =hydrogen, halogen, lower alkyl, aryl-lower alkyl, perfluoro--C.sub.1-20 -alkyl, aryl, substituted aryl, --(CH.sub.2).sub.m --COA or AOC--(CF.sub.2).sub.n,R.sup.7 =hydrogen, lower alkyl, partially or completely halogenated lower alkyl, aryl, substituted aryl or aryl-lower alkyl,A=The residue --OR or NR'.sub.2,R=hydrogen, lower alkyl, aryl, substituted aryl, aryl-lower alkyl or a cation,R'=hydrogen, lower alkyl, aryl, substituted aryl or aryl-lower alkyl,m=a number 0 to 20n=a number 1 to 20,Y=is a specific chiral diphosphine ligand,L=is a neutral ligand selected from ethylene, propylene, cyclooctane, 1,5-hexadiene, norbornadiene, 1,5-cyclooxtadiene, acetonitrile and benzonitrile,p=0, 1 or 2, ando=1 or 2.The invention also describes processes for manufacture of the above complexes. These complexes are used in asymmetric hydrogenations.
    • 本发明描述了具有式[Rh(X)(Y)(Lp)] o的新型手性铑 - 二膦配合物,其中X表示式X-COO-的残基,其中Z表示基团“ 芳基,其中R 1,R 2,R 3 =氢,卤素,低级烷基,芳基 - 低级烷基,全氟C 1-20烷基,芳基,取代的芳基,-OR 7, - (CH 2)m -COA或AOC- CF 2)n,条件是R 1,R 2和R 3中的至少一个表示-OR 7,芳基或取代的芳基,R 4,R 5,R 6 =氢,卤素,低级烷基,芳基 - 低级烷基,全氟-C1-20 - 烷基,芳基,取代的芳基, - (CH 2)m -COA或AOC-(CF 2)n,R 7 =氢,低级烷基,部分或完全卤化的低级烷基,芳基,取代的芳基或芳基 - 低级烷基,A = 残基-OR或NR'2,R =氢,低级烷基,芳基,取代的芳基,芳基 - 低级烷基或阳离子,R'=氢,低级烷基,芳基,取代的芳基或芳基 - 低级烷基,m = 0〜20 n = 1〜20的数,Y =特定的手性二膦配体,L = 选自乙烯,丙烯,环辛烷,1,5-己二烯,降冰片二烯,1,5-环氧丁二烯,乙腈和苄腈,p = 0,1或2,和o = 1或2的中性配体。本发明还描述了 制造上述配合物。 这些络合物用于不对称氢化。
    • 9. 发明授权
    • Catalytic hydrogenation
    • 催化氢化
    • US4544770A
    • 1985-10-01
    • US512845
    • 1983-07-11
    • Emil A. Broger
    • Emil A. Broger
    • C07F9/54
    • C07F9/5435C07F9/5428
    • Compounds of the formula: ##STR1## wherein R.sup.1 is a 2,6,6-trimethyl-1-cyclohexen-1-yl or 2,3,6-trimethylphenyl group, either of which may be unsubstituted or substituted by a hydroxy group or a protected hydroxy group, R.sup.2 is aryl, and X.sup.- is an anionare manufactured by hydrogenating a compound of the formula: ##STR2## wherein R.sup.1, R.sup.2 and X.crclbar. are as above, in an organic solvent or aqueous-organic solvent in the presence of a nickel-, palladium-, platinum-, cobalt-, rhodium-, iridium-, or ruthenium-containing catalyst.The process is suitable as an intermediate step in carotenoid and retinoid syntheses.
    • 下式的化合物:其中R1是2,6,6-三甲基-1-环己烯-1-基或2,3,6-三甲基苯基,其中任一个可以是未取代的或被羟基取代 或保护的羟基,R2是芳基,并且X-是阴离子是通过在有机溶剂或含水溶剂中氢化下式的化合物其中R1,R2和X( - )如上所述, 有机溶剂在镍,钯,铂,钴,铑,铱或钌的催化剂存在下进行。 该方法适合作为类胡萝卜素和类视黄醇合成的中间步骤。