Rh(I)中间体及抗高血压药物用手性催化剂的合成及性能研究  

Synthesis,characterization and catalytic performance of[Rh(COD)(S,S)-Meduphos)]in the antihypertensive drug Ramipril

作　　者：刘桂华 郭旭虎 高安丽 杨军 凡兴强 许明明 余娟 LIU Guihua;GUO Xuhu;GAO Anli;YANG Jun;FAN Xingqiang;XU Mingming;YU Juan(State Key Laboratory of Advanced Technologies for Comprehensive Utilization of Platinum Metals,Yunnan Precious Metals Laboratory Co.Ltd.,Kunming 650106,China)

机构地区：[1]云南贵金属实验室有限公司稀贵金属综合利用新技术国家重点实验室,昆明650106

出　　处：《贵金属》2023年第3期7-12,共6页Precious Metals

基　　金：国家自然科学基金(52361006);云南省转制科研院所技术开发研究专项(202104AR040016);云南省科重大科技专项(202002AB080002、202102AB080007);云南贵金属实验室有限公司科技计划项目(YPML-2022050231)。

摘　　要：在微压状态下,以95%的乙醇为溶剂,三氯化铑、乙烯等为原料,合成了Rh(I)中间体,产率85%;再以该中间体、1,5-环辛二烯、四氟硼酸银和(+)-1,2-双((2S,5S)-2,5-二甲基膦基)苯为原料,四氢呋喃为溶剂合成了Rh(I)手性催化剂,产率91.09%。采用元素分析、^(1)H-NMR、^(13)C-NMR、MS-ESI+和IR对其化学结构进行了表征。以合成抗高血压药物雷米普利为反应模型进行催化活性评价,结果表明,该手性催化剂与商业对照品的催化活性相当,转化率≥70%,产品光学纯度≥98%。Under the condition of micro-pressure,the Rh(I)intermediate was prepared in one-step process from RhCl3·3H2O in 95%ethanol solvent by filling with ethylene gas.The ylied was≥85%.A quqntitative reaction of the Rh(I)intermediate with 1,5-cyclooctandiene,AgBF4 and(S,S)-meduphos in tetrahydrofuran produced the desired chiral catalyst[Rh(COD)(S,S)-Meduphos)]BF_(4) with a yield of 91.09%.The structrues were confirmed by means of elemental analysis,^(1)H-NMR,^(13)C-NMR,FT-IR and MS-ESI+.The catalytic activity in the preparation of Ramipril was found to be≥70%in terms of the conversion rate and optical purity of the product was 98%ee,comparable to the activity and selectivity obtained by using the commercially available catalyst.

关 键 词：二(乙烯)氯铑二聚体 (+)-1 2-双((2S 5S)-2 5-二甲基膦基)苯(1 5-环辛二烯)四氟硼酸铑(I) 合成 结构 催化性能 

分 类 号：O614.8[理学—无机化学]