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

我们已经开发了二（三芳基膦）异位体，2,2 ^'-二（二苯基膦）- 1,1 ^'-二萘基（简称BINAP），并表明其金属配合物作为催化剂对-酰基氨基丙烯酸的不对称氢化和烯丙胺通过1,3 -氢迁移不对称异构化成胺具有很高的效率。我们还报道了Ru (OCOR) _2 （binap）的合成，这是第一个单核binap -Ru （II）配合物，并证明了它们是emanides， α， β和β， γ -不饱和羧酸，烯丙基和均烯丙基醇的不对称加氢的高效催化剂。为了扩大BINAP配体的合成用途，我们继续研究了各种BINAP- ru （II）配合物催化的新型高效不对称反应的开发，总结如下。(1)合成了新型阳离子binap - ru （II）配合物[RuX (binap)（芳烃）]y （X=Cl, Br， I; y =Cl, Br， I, BF_<4'>和BPh_4…More；芳烃=苯和对花香烃），并通过光谱和X射线分析确定了分子结构。我们已经证明这些配合物是各种不饱和底物对映选择性加氢的高效催化剂。特别重要的是这些配合物作为功能化酮的不对称氢化催化剂的高效率。(2)许多取代的BINAP衍生物已被合成。利用这些配合物阐明了控制酮类不对称加氢催化活性和选择性的各种因素。(3)以[RuI (（r - 3,5 -二叔丁基-二叔丁基-二叔丁基）[I]为催化剂，通过动力学拆分完成了2-苄基-甲基-3-羟基丁酸甲酯的高度非对映选择性加氢反应，得到了合成β -内酰胺类抗生素的多功能中间体-甲基(2S， 3r -2-苄基-3-羟基丁酸甲酯（98% 99%）。(4)主要通过氘标记实验，阐明了Ru (OCOCH_3) _2 （bianp）催化α， β -不饱和羧酸的不对称加氢反应机理。(5)制备了新的单位三核配合物[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）配体，并对其在不对称催化中的应用进行了研究。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