浅析一种新型联苯类手性双膦配体的合成

Synthesis of a Novel Chiral Diphosphine Ligand

简述了手性双膦配体的发展简史和新型手性双膦配体SEGPHOS的合成方法。在传统方法的基础上进行关键改进,5-溴胡椒环经格氏反应得到5-胡椒环基氧化二苯基膦、经二(异丙基)氨基锂化后用无水氯化铁氧化偶联合成关键中间体膦氧化物SEGPHOSO_2。"一锅煮"的方法简化了操作过程,特别是后处理更简单,粗品更容易纯化。使用(2S,3S)-二苯甲酰酒石酸进行拆分、最后经三氯氢硅烷还原得到手性双膦配体SEGPHOS。

This paper briefly described the development history of chiral diphosphine ligands. The key improvement based on the traditional synthetic method. The relative phenyl phosphine dioxide was obtained by Grignard reaction from 5-bromo pepper ring compound. Key intermediates of bisphosphine dioxide SEG- PHOSO2 was prepared by oxidative coupling with LDA and anhydrous ferric chloride. The ＂one pot＂ method simplify the operation process, especially the postprocessing was more simple and easier purification of the crude product. Using （2S,3S）- Dibenzoyltartaric acid as optical resolution reagent and by reduction, the chiral SEGPHOS was obtained.