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

开发用于高效不对称合成的新型手性过渡金属催化剂

• 批准号: 01470095
• 负责人: TAKAYA Hidemasa
• 金额: $ 4.74万
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-01470095/
• 关键词: BINAP-Ru; Asymmetric Hydrogenation; Diastereoselective Hydrogenation; Mechanism; [Ru_3X_5(binap)_3]Y; [RuX(binap)(arene)]Y; X-ray analysis; Deuterium-labeled experiment; 不斉触媒反応; BINAP; ルテニウム; αーヒドロキシエステル; 光学活性ラクトン; ヒドロシリル化; 不斉合成; 不斉水素化反応

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

我们已经开发了双(三芳基膦)配体2，2‘-双(二苯基膦)-1，1’-联萘(简称BINAP)，并表明其金属络合物对α-氨基丙烯酸的不对称氢化和烯丙胺1，3-氢迁移生成烯胺的不对称异构化反应具有高效的催化作用。我们还报道了第一个单核BINAP-Ru(II)配合物Ru(OCOR)_2(BINAP)的合成，并证明了它们对酰胺、α、β和β、伽马不饱和羧酸、烯丙醇和高烯丙醇的不对称氢化反应是高效的催化剂。为了扩大BINAp配体的合成用途，我们继续对各种BINAp-Ru(II)配合物催化的新型高效不对称反应的开发进行了研究，总结如下：(1)新的阳离子BINAp-Ru(II)配合物[Rux(BINAp)(芳烃)]y(X=氯、溴和I；Y=氯、溴、I、BF_&lt；4‘&gt；和BPh_4…此外，高产率地合成了芳烃(芳烃=苯和对伞花烃)，并通过光谱分析和X-射线分析确定了其分子结构。我们已经证明这些配合物是各种不饱和底物对映体选择性氢化的高效催化剂。尤其重要的是这些配合物作为功能化酮的不对称氢化催化剂具有很高的效率。(2)合成了一系列取代的BINAP衍生物。(3)以[RuI((R-3，5-二叔丁基-BINAP)(p-伞花烃)]I为催化剂，合成β-内酰胺类抗生素的中间体(2S，3R-2-苯甲酰胺甲基-3-羟基丁酸甲酯))，实现了2-苯甲胺甲基-3-氧丁酸甲酯的动态动力学拆分非对映选择性氢化反应。(4)不对称氢化反应机理本文主要通过氚标记实验对Ru(OCOCH_3)_2(Bianp)催化的β-不饱和羧酸进行了研究。(5)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(三芳基膦)配体，并考察了它们在不对称催化反应中的应用。较少

项目成果

N.Fukuda,K.Mashima,Y.Matsumura,H.takaya: "Synthesis of New Chiral Bis(triarylphosphine) Ligands Based on Asymmetric Hydrogenation of 4.5ーDiarylー2ーoxocyclopentanecarboxylates." Tetrahedron Lett.31. 7185-7188 (1990)

N.Fukuda、K.Mashima、Y.Matsumura、H.takaya：“基于 4.5-二芳基-2-氧代环戊烷甲酸酯的不对称氢化合成新型手性双（三芳基膦）配体。31”（1990 年）。 ）

K. Mashima, Y. Matsumura, K. Kusano, H. Kumobayashi, N. Sayo, Y. Hori, T. Ishizaki, S. Akutagawa, and H. Takaya: "Highly Stereoselective Asymmetric Hydrogenation of 2-Benzamidomethyl-3-oxobutanoate Catalyzed by Cationic BINAP-Ruthenium(II) Complexes" J. C

K. Mashima、Y. Matsumura、K. Kusano、H. Kumobayashi、N. Sayo、Y. Hori、T. Ishizaki、S. Akutakawa 和 H. Takaya：“2-苯甲酰氨基甲基-3-氧代丁酸酯的高度立体选择性不对称氢化

H.Takaya,T.Ohta,S.Inoue,R.Noyori: "Asymmetric Hydrogenation of Allylic Alcohols Using BINAPーRuthenium Complexes" Org.Synth.,.

H.Takaya、T.Ohta、S.Inoue、R.Noyori：“使用 BINAP-钌配合物对烯丙醇进行不对称氢化”Org.Synth.,。

K.Mashima,Y.Matsumura K.Kusano,H.Kumobayashi N.Sayo,Y.Hori,T.Ishizaki,S.Akutagawa H.Takaya: "Highly Steoselective Asymmetric Hydrogenation of 2ーBenzamidomethylー3ーoxobutanoate Catalyzed by Cationic BINAPーRuthenium(II)Compleses" J.Chem.Soc.,Chem.Commun.

K.Mashima,Y.Matsumura K.Kusano,H.Kumobayashi N.Sayo,Y.Hori,T.Ishizaki,S.Akutakawa H.Takaya：“阳离子 BINAP 催化的 2-苯甲酰氨基甲基-3-氧代丁酸酯的高度立体选择性不对称氢化-钌(II) 完成”J.Chem.Soc.、Chem.Commun。

H.Takaya,T.Ohta,S.Inoue,R.Noyori: "Asymmetric Hydrogenation of Allylic Alcohols Using BINAPーRuthenium Compleses" Org.Synth.

H.Takaya、T.Ohta、S.Inoue、R.Noyori：“使用 BINAP-钌完成烯丙醇的不对称氢化”Org.Synth。