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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Development of a novel chiral palladacycle and its application in asymmetric hydrophosphination reaction?
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Development of a novel chiral palladacycle and its application in asymmetric hydrophosphination reaction?

机译：新型手性帕拉达环的开发及其在不对称加氢磷酸化反应中的应用？

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摘要

A novel amine ligand, 1-(2,5-dichlorophenyl)-N,N-dimethylethanamine, was synthesized from 1-(2,5- dichlorophenyl)ethanone via a three step synthetic route. Direct ortho-palladation of the amine ligand with Pd(OAc)~2 gave the racemic dimeric complex in high yield. This racemic palladacycle was efficiently resolved through the formation of its (S)-prolinato derivatives. The resulting diastereomeric complexes were separated efficiently by column chromatography. In the solid state, the structure and absolute configuration of the two optically resolved palladium complexes were determined by single crystal X-ray crystallography. In solution, their absolute conformations were also investigated by the 2D ~1H-~1H rotating frame nuclear Overhauser enhancement (ROESY) NMR spectroscopy. Both (R,R) and (S,S)-di-μ-chloro dimeric palladium complexes could be obtained chemoselectively by treating the corresponding prolinato derivatives with dilute hydrochloric acid. The amine auxiliary could be subsequently removed from the palladium center by treatment with concentrated hydrochloric acid. The enantiomerically pure palladacycle was used to promote the asymmetric hydrophosphination reaction between diphenylphosphine and dimethyl acetylenedicarboxylate. The ~(31)P{~1H} NMR spectroscopy indicated that only one stereo-isomeric product was formed.
机译：通过三步合成路线，由1-（2,5-二氯苯基）乙酮合成了一种新型的胺配体1-（2,5-二氯苯基）-N，N-二甲基乙胺。胺配体与Pd（OAc）〜2的直接邻位钯制得外消旋二聚体复合物，收率很高。通过形成其（S）-脯氨酸衍生物，可有效拆分该外消旋的palladacycle。所得非对映体复合物通过柱色谱法有效分离。在固态下，两种光学拆分的钯配合物的结构和绝对构型通过单晶X射线晶体学测定。在溶液中，还通过2D〜1H-〜1H旋转框架核Overhauser增强（ROESY）NMR光谱研究了它们的绝对构象。 （R，R）和（S，S）-二-μ-氯二聚钯配合物都可以通过用稀盐酸处理相应的脯氨酰胺衍生物来化学选择性地获得。随后可以通过用浓盐酸处理将胺助剂从钯中心除去。对映体纯的palladacycle用于促进二苯基膦和乙炔二羧酸二甲酯之间的不对称氢磷酸化反应。 〜（31）P {〜1H} NMR光谱表明仅形成一种立体异构产物。

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