(R)-(-)-1-[(S)-2-二苯基膦二茂铁]乙基二叔丁基膦的合成  

Synthesis of R-(-)-1-[(S)-2-(Diphenylphosphine) Ferrocenyl] Fthyl Di-tert-butyl Phosphine

作　　者：赵顺伟[1] 刘婷婷 陈瑨[1] 周铎[1] 张垚 陈辉[1] ZHAO Shun-wei;LIU Ting-ting;CHEN Jin;ZHOU Duo;ZHANG Yao;CHEN Hui(Institute of Chemistry Henan Academy of Sciences,Zhengzhou 450002,Henan,China)

机构地区：[1]河南省科学院化学研究所有限公司,河南郑州450002

出　　处：《合成材料老化与应用》2020年第5期51-52,66,共3页Synthetic Materials Aging and Application

基　　金：河南省科学院科研开发项目(200403001,200503001,200603035,200603041)。

摘　　要：以乙酰基二茂铁为原料,经过手性催化还原高选择性得到乙醇基二茂铁,通过酯化、胺解得到R-N,N-二甲基-1-二茂铁乙胺,再经过锂化后与二苯基氯化膦反应得到N,N-二甲基-(R)-1-[(S)-2-(二苯基膦)二茂铁基]乙胺,最后与二叔丁基膦发生构型保持的取代反应,得到高立体选择性的双膦配体R-(-)-1-[(S)-2-(二苯基膦)二茂铁]乙基二叔丁基膦,总收率20%,产品结构经过氢谱、碳谱、膦谱确证,手性高效液相色谱分析其ee值高达99%。In this study, the master ethanol-based ferrocene was obtained from acetyl ferrocene thr-ough chiral catalytic reduction.Then, R-N,N-dimethyl-1-ferrocene ethylamine was obtained through esterification and amine hydrolysis.After lithium, the compound reacted with diphenyl phosphine chloride to get N,N-dimethyl-(R)-1-[(S)-2-(diphenyl phosphine) ferrocene] ethylamine.To study the configuration-invariant chemical substitution of the final compound with ditertbutylphosphine to obtain a highly stereoselective bisphosphine ligand R-(-)-1-[(S)-2-(diphenylphosphine) ferrocenyl] ethyl di-tert-butyl phosphine.The overallyield of the reaction was 20%, and the product structure was determined by NMR and other methods.The EE value was up to 99% by chiral HIGH performance liquid chromatography.

关 键 词：乙酰基二茂铁 手性催化还原 R-(-)-1-[(S)-2-(二苯基膦)二茂铁]乙基二叔丁基膦 

分 类 号：O627.6[理学—有机化学]