Development of New Chiral Transition-Metal Catalysts for Highly Efficient Asymmetric Synthesis

我们已经开发了一种阻转异构的双（三芳基膦）配体2，2 ^'-双（二苯基膦基）-1，1 ^'-联萘（BINAP），并证明其金属配合物作为催化剂对-酰胺基丙烯酸的不对称氢化和烯丙胺的1，3-氢迁移不对称异构化具有很高的催化活性。我们还报道了第一个单核BINAP-Ru（II）配合物Ru（OCOR）_2（binap）的合成，并证明了它们是高效的不对称氢化反应的催化剂，用于emanides，α，β-和β，γ-不饱和羧酸，烯丙醇和高烯丙醇的不对称氢化反应。为了扩大BINAP配体的合成用途，我们继续研究开发由各种BINAP-Ru（II）络合物催化的新的高效不对称反应，这些络合物总结如下。(1)新的阳离子BINAP-Ru（II）配合物[RuX（binap）（arene）]y（X=Cl，Br，I ; Y = Cl，Br，I，BF_（4 '），BPh_4 ...更多信息 芳烃=苯和对伞花烃），并通过光谱和X-射线分析确定了其结构。我们已经表明，这些配合物是各种不饱和底物的对映选择性氢化的高效催化剂。特别重要的是这些配合物作为官能化酮的不对称氢化催化剂的高效率。(2)已经合成了许多取代的BINAP衍生物。利用这些配合物，阐明了控制酮不对称加氢催化活性和选择性的各种因素。(3)以[RuI（（R-3，5-di-tert-Bu-binap）（p-cymene）] I为催化剂，通过动态动力学拆分实现了2-苯甲酰氨基甲基-3-氧代丁酸甲酯的高非对映选择性氢化，得到了β-内酰胺类抗生素的多用途中间体（2S，3R-2-苯甲酰氨基甲基-3-羟基丁酸甲酯（98%~ 99%）。(4)以氘标记实验为主要手段，研究了Ru（OCOCH_3）_2（bianp）催化α，β-不饱和羧酸不对称氢化反应的机理。(5)本文合成了新的单阳离子三核配合物[Ru_3X_5（binap）_3] Y，并讨论了它们在催化反应中的作用。(6)合成了几种新的双（三芳膦）配体，并研究了它们在不对称催化中的应用。少

We had already developed atroisomeric bis (triarylphosphine) ligand, 2, 2^'-bis (diphenylphosphino)-1, 1^'-binaphthyl (abbreviated to BINAP) and showed that its metal complexes had high efficiency as catalysts for asymmetric hydrogenation of -acylaminoacrylic acids and asymmetric isomerization of allylamines into enamines by 1, 3-hydrogen migration. We also reported synthesis of Ru (OCOR) _2 (binap), the first mononuclear BINAP-Ru (II) complexes, and demonstrated that they are highly efficient catalysts for the asymmetric hydrogenations of emanides, alpha, beta- and beta, gamma-unsaturated carboxylic acids, allylic and homoallylic alcohols. In order to expand the synthetic utility of BINAP ligand, we have continued our investigation on the development of new highly efficient asymmetric reactions catalyzed by various BINAP-Ru (II) complexes which have been summarized below.(1) New cationic BINAP-Ru (II) complexes [RuX (binap) (arene)]y (X=Cl, Br, and I ; Y = Cl, Br, I, BF_<4'> and BPh_4 … More ; arene = benzene and p-cymene) have been synthesized in high yields and the molecular structures have been determined by spectroscopic and X-ray analyses. We have shown that these complexes are highly efficient catalysts for enantioselective hydrogenation of various unsaturated substrates. Especially important is the high efficiency of these complexes as catalysts for asymmetric hydrogenation of functionalized ketones.(2) A number of substituted BINAP derivatives have been synthesized. Various factors controlling the catalytic activity and selectivity of the asymmetric hydrogenation of ketones have been elucidated by use of these complexes.(3) Highly diastereoselective hydrogenation of methyl 2-benzamidomethyl-3-oxobutanoate via dynamic kinetic resolution has been accomplished by using [RuI ((R-3, 5-di-tert-Bu-binap) (p-cymene)] I as catalyst, giving methyl (2S, 3R-2-benzamidomethyl-3-hydroxybutanoate (98% 99%), a versatile intermediate intermediate for the synthesis of beta-lactam antibiotics.(4) Mechanism of asymmetric hydrogenation of alpha,beta-unsaturated carboxylic acids catalyzed by Ru (OCOCH_3) _2 (bianp) has been elucidated based mainly on deuterium-labeled experiments.(5) New monocationic trinuclear complexes [Ru_3X_5 (binap) _3] Y have been prepared and their roles in catalytic reactions have been discussed.(6) Several new bis (triaryphophine) ligands have been synthesized and their use for asymmetric catalysis have been investigated. Less