Biphenyldiphosphine compounds
    2.
    发明授权
    Biphenyldiphosphine compounds 有权
    联苯二膦化合物

    公开(公告)号:US07094725B2

    公开(公告)日:2006-08-22

    申请号:US10888820

    申请日:2004-07-09

    IPC分类号: B01J31/00

    摘要: The present invention provides compounds of the formula wherein R is optionally substituted lower alkyl, cycloalkyl or aryl; R′ is alkyl or aryl; n is zero or an integer of 1 or 2; or an enantiomer thereof; or an enantiomeric mixture thereof. The compounds of formula (I) are bridged C2-symmetric biphenyldiphosphine analogs and, thus, may be employed as ligands to generate chiral transition metal catalysts which may be applied in a variety of asymmetric reactions. The compounds of the present invention are easily accessible in high diastereomeric and optical purity according to the methods disclosed herein.

    摘要翻译: 本发明提供下式的化合物其中R是任选取代的低级烷基,环烷基或芳基; R'是烷基或芳基; n为0或1或2的整数; 或其对映体; 或其对映体混合物。 式(I)化合物是桥连的C 2 - 对称联苯基二膦类似物,因此可用作配体以产生可用于各种不对称反应的手性过渡金属催化剂。 根据本文公开的方法,本发明的化合物可以以高非对映异构体和光学纯度容易地获得。

    Chiral pyridylphosphines and their application in asymmetric catalytic
hydrogenation of 2-arylpropenoic acids
    6.
    发明授权
    Chiral pyridylphosphines and their application in asymmetric catalytic hydrogenation of 2-arylpropenoic acids 失效
    手性吡啶基膦及其在2-芳基丙烯酸的不对称催化氢化中的应用

    公开(公告)号:US5886182A

    公开(公告)日:1999-03-23

    申请号:US988376

    申请日:1997-12-10

    IPC分类号: C07F9/58 C07F9/6568 C07F9/50

    CPC分类号: C07F9/65683 C07F9/587

    摘要: Novel, optically active phosphorous compounds of the formula, ##STR1## wherein R.sup.1 represents hydrogen atoms, straight or branched-chain alkyl groups having from 1 to 6 carbon atoms, R.sup.2 represents hydrogen atoms, halogen atoms, lower alkyl groups (1 to 6 carbon atoms), lower alkoxy groups (1 to 6 carbon atoms), hydroxy group, chiral hydroxyalkyl groups, and amino groups (1.degree., 2.degree., 3.degree.) vinyl groups or allyl groups and R.sup.3 represents phenyl groups, aryl groups, cyclohexyl groups, substituted and unsubstituted cycloalkyl groups, heteroaromatic rings, are described. The compounds of the formula serve as highly useful ligands in the preparation of ruthenium complexes which are effective catalysts for the asymmetric hydrogenation of 2-arylpropenoic acids leading to high valued 2-arylpropionic acids.

    摘要翻译: 新型的具有下式的光学活性的磷化合物,其中R1代表氢原子,具有1-6个碳原子的直链或支链烷基,R2代表氢原子,卤素原子,低级烷基(1-6个碳原子) 原子),低级烷氧基(1至6个碳原子),羟基,手性羟基烷基和氨基(1,2,3)乙烯基或烯丙基,R 3表示苯基,芳基,环己基 ,取代和未取代的环烷基,杂芳环。 该配方的化合物在钌配合物的制备中起着非常有用的配体作用,这是用于2-芳基丙烯酸的不对称氢化的有效催化剂,导致高价值的2-芳基丙酸。

    Chiral aminophosphines
    7.
    发明授权
    Chiral aminophosphines 有权
    手性氨基膦

    公开(公告)号:US5952527A

    公开(公告)日:1999-09-14

    申请号:US241091

    申请日:1999-02-01

    摘要: This invention relates to (R)- and (S)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2,2'-diamine (R-1 and S-1) and (R)- and (S)-2,2'-bis(diarylphospinoamino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl (R-2 and S-2) and (R)- and (S)-2,2'-bis(diaklphospinoamino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl (R-3 and S-3); to a process for the preparation of R-1 and S-1 in which (R) or (S)-1,1'-binaphthyl-2,2'-diamine is partially hydrogenated in the presence of Adam's catalyst (5-20 wt/o of starting material) at 20-100.degree. C. for 20-100 hours in glacial acetic acid (solvent); to a process for the preparation of R-2, S-2, R-3 and S-3 in which R-1 or S-1 is reacted with chlorodiarylphosphine or chlorodialkylphosphine in the presence of n-butyllithium; and to the rhodium complexes containing 2 or 3 as effective catalysts for the asymmetric hydrogenation of prochiral substrates such as olefins to produce higher valued chiral products; and to the asymmetric catalytic hydrogenation of enamides under mild conditions using the Rh-(2) or Rh-(3) as catalyst with chemical yields as high as 100% and enantiomeric excess (e.e.) as high as 99%.

    摘要翻译: 本发明涉及(R) - 和(S)-5,5',6,6',7,7',8,8'-八氢-1,1'-联萘-2,2'-二胺(R -1和S-1)和(R) - 和(S)-2,2'-双(二芳基磷酰氨基)-5,5',6,6',7,7',8,8'-八氢-1 ,1'-联萘(R-2和S-2)和(R) - 和(S)-2,2'-双(二烷基氨基)-5,5',6,6',7,7',8 ,8'-八氢-1,1'-联萘(R-3和S-3); 涉及制备R-1和S-1的方法,其中(R)或(S)-1,1'-联萘-2,2'-二胺在Adam催化剂存在下部分氢化(5-20 wt / o的原料)在20-100℃下在冰乙酸(溶剂)中反应20-100小时; 涉及制备R-2,S-2,R-3和S-3的方法,其中R-1或S-1与氯二芳基膦或氯二烷基膦在正丁基锂存在下反应; 以及含有2或3的铑络合物作为用于前置手性底物如烯烃的不对称氢化的有效催化剂,以产生更高价值的手性产物; 和使用Rh-(2)或Rh-(3)作为催化剂的温和条件下的酰胺的不对称催化氢化,化学产率高达100%,对映体过量(e.e。)高达99%。

    Chiral aminophosphines
    8.
    发明授权
    Chiral aminophosphines 失效
    手性氨基膦

    公开(公告)号:US5919981A

    公开(公告)日:1999-07-06

    申请号:US988377

    申请日:1997-12-10

    摘要: This invention relates to (R)- and (S)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl-2,2'-diamine (R-1 and S-1) and (R)- and (S)-2,2'-bis(diarylphospinoamino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl (R-2 and S-2) and (R)- and (S)-2,2'-bis(dialkylphospinoamino)-5,5',6,6',7,7',8,8'-octahydro-1,1'-binaphthyl (R-3 and S-3); to a process for the preparation of R-1 and S-1 in which (R) or (S)-1,1'-binaphthyl-2,2'-diamine is partially hydrogenated in the presence of Adam's catalyst (5-20 wt % of starting material) at 20-100.degree. C. for 20-100 hours in glacial acetic acid (solvent); to a process for the preparation of R-2, S-2, R-3 and S-3 in which R-1 or S-1 is reacted with chlorodiarylphosphine or chlorodialkylphosphine in the presence of n-butyllithium; and to the rhodium complexes containing 2 or 3 as effective catalysts for the asymmetric hydrogenation of prochiral substrates such as olefins to produce higher valued chiral products; and to the asymmetric catalytic hydrogenation of enamides under mild conditions using the Rh-(2) or Rh-(3) as catalyst with chemical yields as high as 100% and enantiomeric excess (e.e.) as high as 99%.

    摘要翻译: 本发明涉及(R) - 和(S)-5,5',6,6',7,7',8,8'-八氢-1,1'-联萘-2,2'-二胺(R -1和S-1)和(R) - 和(S)-2,2'-双(二芳基磷酰氨基)-5,5',6,6',7,7',8,8'-八氢-1 ,1'-联萘(R-2和S-2)和(R) - 和(S)-2,2'-双(二烷基磷酰氨基)-5,5',6,6',7,7',8 ,8'-八氢-1,1'-联萘(R-3和S-3); 涉及制备R-1和S-1的方法,其中(R)或(S)-1,1'-联萘-2,2'-二胺在Adam催化剂存在下部分氢化(5-20 重量%的原料)在20-100℃下在冰乙酸(溶剂)中反应20-100小时; 涉及制备R-2,S-2,R-3和S-3的方法,其中R-1或S-1与氯二芳基膦或氯二烷基膦在正丁基锂存在下反应; 以及含有2或3的铑络合物作为用于前置手性底物如烯烃的不对称氢化的有效催化剂,以产生更高价值的手性产物; 和使用Rh-(2)或Rh-(3)作为催化剂的温和条件下的酰胺的不对称催化氢化,化学产率高达100%,对映异构体过量(e.e。)高达99%。

    Chiral tertiary aminoalkylnaphthols
    9.
    发明授权
    Chiral tertiary aminoalkylnaphthols 失效
    手性叔氨基烷基萘酚

    公开(公告)号:US07674900B2

    公开(公告)日:2010-03-09

    申请号:US11578708

    申请日:2005-05-11

    IPC分类号: C07F9/6544

    摘要: The present invention provides bipyrimidinyl diphosphine compounds of the formula wherein R is optionally substituted alkyl, cycloalkyl, aryl or heteroaryl; R′ and R″ are independently optionally substituted alkyl, cycloalkyl, aryl or heteroaryl; or an enantiomer thereof; or an enantiomeric mixture thereof. The compounds of the formula (I) are chiral atropisomeric bipyrimidinyl diphosphine compounds and, thus, may be employed as ligands to generate chiral transition metal catalysts which may be applied in a variety of asymmetric reactions, e.g., in palladium catalyzed asymmetric allylic substitution reactions. The compounds of the present invention are easily accessible in high enantiomeric purity according to the methods disclosed herein.

    摘要翻译: 本发明提供下式的二嘧啶基二膦化合物其中R是任选取代的烷基,环烷基,芳基或杂芳基; R'和R“独立地是任选取代的烷基,环烷基,芳基或杂芳基; 或其对映体; 或其对映体混合物。 式(I)的化合物是手性的不对称双嘧啶基二膦化合物,因此可以用作配体以产生手性过渡金属催化剂,其可以用于各种不对称反应,例如钯催化的不对称烯丙基取代反应。 根据本文公开的方法,本发明的化合物可以以高对映体纯度容易地获得。