Chiral aminophosphines
    1.
    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
    2.
    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%。