Catalytic Asymmetric Reactions Means of Attractive Interactions

催化不对称反应是有吸引力的相互作用的手段

• 批准号: 07454163
• 负责人: HAYASHI Tamio
• 金额: $ 4.93万
• 依托单位: Kyoto University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07454163/
• 关键词: Catalytic Asymmetric Synthesis; Attractive Interactions; Chiral Monophosphines; Chiral Ferrocenylphosphines; Chiral Bisoxazolines; Asymmetric Oxidation; Asymmetric Substitutions; 光学活性単座配位子; ワッカー型反応; MOP配位子; 軸不斉ビナフチル; 光学活性ビスオキサゾリン; boxax配位子; 不

Asymmetric reactions catalyzed by transition metal complexes containing optically active phosphine ligands have attracted significant interest for their synthetic utility. One of the most exciting and challenging subjects in research on the catalytic asymmetric synthesis is development of the chiral ligand which will fit in with a given reaction efficiently in enantioselectivity as well as in catalytic activity. In designing chiral ligands we have attached importance to introduction of a functional group into the ligand that, where possible, would be expected to interact attractively with a functional group in the substrate. The attractive interactions will enhance the enantioselectivity in catalytic asymmetric reactions by increased steric interactions between the chiral ligand and a prochiral substrate. We have developed new chiral ligands bearing some functional groups on the backbone : 1) 2- (Diphenylphosphino) -1,1'-binaphthyls (MOPs) which have carboxyl, hydroxy, alkoxy, and amino groups on the 2'-position. 2) Ferrocenyl-and ruthenocenylbisphosphines containing amino and hydroxy groups on the metallocene side chain. 3) Several kinds of functional groups were introduced into 3-and 3'-positions of 2,2'-bis [4- (alkyl) oxazol-2-yl] -1,1'-binaphthyls (boxax). These functionalized chiral ligands have been used for palladium-catalyzed asymmetric reactions including allylic substitutions and Wacker-type cyclization.

由含有光学活性膦配体的过渡金属复合物催化的不对称反应引起了对其合成效用的重大兴趣。关于催化不对称合成的研究中，最令人兴奋和最具挑战性的受试者之一是手性配体的发展，这将有效地适合给定的反应以及对映选择性和催化活性。在设计手性配体时，我们对将功能组引入配体的引入非常重要，这些功能组将在可能的情况下与底物中的功能组相互作用。有吸引力的相互作用将通过手性配体与手持底物之间的空间相互作用增加催化不对称反应的对映选择性。我们已经开发了新的手性配体在骨架上有一些官能团：1）2-（二苯基磷酸）-1,1'-二磷酸（MOPS），它们在2'-position上含有羧基，羟基，碱和氨基组。 2）在甲金属元的侧链上含有氨基和羟基的甲基苯基和氟苯基苯基二磷。 3）将几种官能团引入了3'位置，为2,2'-双[4-（烷基）恶唑-2-基] -1,1'-Binaphyphyls（Boxax）。这些功能化的手性配体已用于钯催化的不对称反应，包括烯丙基取代和Wacker型环化。

项目成果

魚住泰広: "Catalytic Asymmetric Wacker-Type Cyclization" J. Am. Chem. Soc.(in press).

Yasuhiro Uozumi：“催化不对称瓦克型环化”J. Am.（正在出版）。

林 民生: "Ferrocenes" VCH Verlagsgesellshaft, 1-540 (1995)

Tamio Hayashi：“二茂铁”VCH Verlagsgesellshaft，1-540 (1995)

林 民生: "Erythro-Selective Aldol-Type Reaction of N-Sulfonylaldimines with Methyl Isocyanoacetate Catalyzed by Gold (I)" Tetrahedron Lett.37. 4969-4972 (1996)

Tamio Hayashi：“金 (I) 催化的 N-磺酰亚胺与异氰乙酸甲酯的红选择性醇醛型反应”Tetrahedron Lett.37 4969-4972 (1996)。

林民生: "Ferrocenes" VCH Verlagsgesellshaft, 1-540 (1995)

Tamio Hayashi：“二茂铁”VCH Verlagsgesellshaft，1-540 (1995)

林 民生: "Catalytic Asymmetric Hydrosilylation of Ketones with New Chiral Ferrocenylphosphine-Imine Ligands" Tetrahedron Asymmetry. 6. 2503-2506 (1995)

Tamio Hayashi：“用新型手性二茂铁基膦-亚胺配体催化酮的不对称氢化硅烷化”四面体不对称性。 6. 2503-2506 (1995)