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The New industrial use of a metal Compound bis - optically Active phosphine as Catalyst for homogeneous Asymmetric hydrogenation reactions

机译:金属化合物双光学活性膦在均相不对称加氢反应中的新工业应用

摘要

Optically active phosphines of formula (I) are new: A-P(B)-CH2.CH2-P(B)-A (I) (A and B are opt. substd 1-12C alkyl, 4-7C cycloalkyl or aryl abut A and B must be different and not interfere with the steric conditions around the C atoms). Catalysts for homogeneous reactions comprise (a) Rh, Ir or Ru and (b) 0.5-2 moles per mole metal of (I). Processes for stereoselective hydrogenation of beta-substd alpha-acylamidoacrylic acids (II) or their salts, esters and amides using these catalysts are also claimed. The tetrafluoroborate of cycloocta-1,5-diene 1,2-bis(o-anisylphenyl phosphino)ethane rhodium and solns contg bis (cycloocta-1,5-diene) dichlorodirhodium and 1,2-bis(o-anisylphenylphosphino)ethane. wherein the phosphine is optically active, are also new. The catalysts contg (I) as ligands agive hydrogenations of high stereospecificity. Prods include alanine, valine, 3-(3,4-dihydroxyphenyl)-L-alanine (i.e L-DOPA) and esp. substd phenylalanines obtd by reducing (II) produced by hydrolysis of azolactones during Erlenmeyer's synthesis.
机译:式(I)的光学活性膦是新的:AP(B)-CH2.CH2-P(B)-A(I)(A和B分别取代1-12C烷基,4-7C环烷基或芳基,A邻接)和B必须不同,并且不得干扰C原子周围的空间条件。用于均相反应的催化剂包括(a)Rh,Ir或Ru和(b)每摩尔(I)金属0.5-2摩尔。还要求保护使用这些催化剂的β-取代的α-酰基酰胺基丙烯酸(II)或其盐,酯和酰胺的立体选择性加氢的方法。环辛-1,5-二烯1,2-双(邻苯甲酰基苯基膦基)乙烷铑的四氟硼酸盐和含双(环辛-1,5-二烯)二氯吡啶鎓和1,2-双(邻苯甲酰基苯基膦基)乙烷的溶液。其中膦是光学活性的,也是新的。 (I)作为配体的催化剂可实现高立体特异性的氢化反应。产品包括丙氨酸,缬氨酸,3-(3,4-二羟基苯基)-L-丙氨酸(即L-DOPA)和esp。通过还原在艾伦迈尔合成过程中由偶氮内酯水解产生的(II),从而取代了苯丙氨酸。

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