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

基本信息

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

项目摘要

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.

我们最初的计划综合[2.2] paracyclophanebisphasphine配体是为了二聚桥式双（p-xylylene）中间体，以选择性地实现所需的伪 - 官方distuditution。 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]美国默克（Merck）研究小组报道了paracicclanebisphasphinium- ruthenium-弦丁和钯络合物。在我们的初步研究中，无论是在理论上还是在实验上，我们都得出了这样的结论：溴蒸气和粉状粉[2.2]旁获得性的气体固定反应将是伪-orreso-ortho的选择性。现在正在进行矫正条件的改善。当相关的C2手性环烷配体时，我们成功地衍生出源自环状TR_GER碱基的二齿氮配体的合成和分辨率。