Development of Transition Metal Catalysts with Optical Active [2.2] Paracyclophanebisphosphine Ligands

光学活性过渡金属催化剂的研制[2.2]对环芳双膦配体

• 批准号: 09640639
• 负责人: MIYAHARA Yuji
• 金额: $ 1.98万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640639/
• 关键词: cyclophane; phosphine ligand; transition metal complexes

Our initial plan to synthesize the [2.2]paracyclophanebisphosphine ligand was to dimerize a bridged bis(p-xylylene) intermediate to realize the desired pseudo-ortho disubstitution selectively. Although the precursor of the reaction intermediate was prepared smoothly via a newly developed route, the intramolecular version of the dimerization failed, possibly due to difficulty of generating the bis(p-xylylene) intermediate.While we were examining the reaction conditions for selective introductionm of two bromine atoms in a pseudo-ortho fashon, exactly the same project dealing with the synthesis and catalytic activity of [2.2]paracyclophanebisphosphine- ruthenium and palladium complexes was reported by a Merck research group in U.S.A.However, the bottleneck of their synthetic route was the tedius separation of the pseudo-ortho dibromide from a complex mixture of bromination products. In our preliminary studies, both theoretically and expermentally, we arrived at the conclusion that gas-solid reaction between bromine vapor and powdered [2.2]paracyclophane would be pseudo-ortho selective. Improvement of the rection conditions is now underway.As the related C2 chiral cyclophane ligands, we succeeded in the synthesis and resolution of bidentate nitrogen ligands derived from cyclic Tr_ger bases.

我们合成[2.2]对环芳双膦配体的最初计划是二聚桥接双（对亚二甲苯基）中间体以选择性地实现所需的伪邻位双取代。尽管通过新开发的路线顺利制备了反应中间体的前体，但分子内的二聚反应失败了，可能是由于难以产生双当我们检查以假邻位方式选择性引入两个溴原子的反应条件时，美国的Merck研究小组报道了涉及[2.2]对环凡双膦-钌和钯络合物的合成和催化活性的完全相同的项目。然而，其合成路线的瓶颈是从溴化产物的复杂混合物中分离假邻位二溴化物的繁琐过程。在我们的初步研究中，从理论和实验两方面得出了溴蒸气与粉末状[2.2]对环芳之间的气-固反应是假邻位选择性的结论。作为相关的C2手性环蕃配体，我们成功地合成和拆分了由环状Tr_格尔碱衍生的双齿氮配体。

项目成果

A.A.Ibrahim: "Synthesis and Properties of A New Series of Trogerophanes" Journal of Heterocyclic Chemistry. 35・1. 209-215 (1998)

A.A.Ibrahim：“新系列 Trogerophanes 的合成和性能”杂环化学杂志 35・1（1998）。

Y. Miyahara: "Novel C2 Chiral Diamine Ligands Derived from Cyclic Troger Bases" Tetrahedron Letters. 40・9. 1705-1708 (1999)

Y. Miyahara：“源自环状 Troger 碱基的新型 C2 手性二胺配体”四面体快报 40・9 (1999)。

A.A.Ibrahim: "Synthesis and Properties of A New Series of Trogerophanes" J.Heterocycl.Chem.35 (1). 209-215 (1998)

A.A.Ibrahim：“新系列 Trogerophanes 的合成和特性”J.Heterocycl.Chem.35 (1)。

Y.Miyahara: "Novel C2 Chiral Diamine Ligands Derived from Cyclic Troger Bases" Tetrahedron Lett.40 (9). 1705-1708 (1999)

Y.Miyahara：“从环状 Troger 碱基衍生的新型 C2 手性二胺配体”Tetrahedron Lett.40 (9)。

Y.Miyahara: "Novel C2 Chiral Diamine Ligands Derived from Cyclic Troger Bases" Tetrahedron Letters. 40・9. 1705-1708 (1999)

Y.Miyahara：“源自环状 Troger 碱基的新型 C2 手性二胺配体”四面体快报 40・9 (1999)。