摘要
设计合成了一种同时具有平面手性与两个中心手性的结构新颖的、空间立体效应和电子效应精细可调的手性二茂铁P,N配体,拓宽二茂铁P,N配体的应用范围.以(R)-Ugi′s胺为起始原料,经正丁基锂锂化上膦、与酸酐反应、氨解反应、与苯乙酮衍生物反应、硼氢化钠还原反应,共5步反应得到一系列新型的多手性中心的二茂铁P,N配体,其结构经1H NMR,13C NMR和MS(ESI)表征.将该手性配体用于苯甲醛亚胺酯与马来酸二甲酯的不对称1,3偶极环加成反应中,在最优的反应条件下:以AgOAc/5a为催化剂,碳酸钾为碱,二氯甲烷为溶剂,0℃反应,得到endo构型的环加成产物,收率高达90%和对映选择性为92%ee.
A novel chiral ferrocene P,N ligands with both planar chiral and two central chiral structures,with fine adjustable spatial stereoscopic effects and electronic effects were designed and synthesized,so as to broaden the application range of ferrocene P,N ligands.A series of novel multi-chiral ferrocene P,N ligands were synthesized from(R)-Ugi′s amine by five steps,firstly R-Ugi′s amine activating by n-butyl lithium to introduce the phosphine group,secondly,reaction with anhydride,ammonolysis,thirdly,reaction with acetophenone derivatives,and finally,reduction with sodium borohydride.The structures were confirmed by1H NMR,13C NMR,ESI-MS.The chiral ligands were used in the asymmetric 1,3-dipolar cycloaddition reaction of azomethine ylide and dimethyl maleate.Under the optimal reaction conditions:using AgOAc/5a as catalyst,potassium carbonate as base,dichloromethane as solvent and 0℃,the endo cycloaddition product was obtained.The yield was up to 90%and the enantioselectivity was 92%ee.
作者
任金娜
薛志勇
REN Jinna;XUE Zhiyong(College of Chemistry and Chemical Engineering, Wuhan Textile University, Wuhan 430073, China)
出处
《湖北大学学报（自然科学版）》
CAS
2020年第6期656-661,共6页
Journal of Hubei University：Natural Science
基金
国家自然科学基金(21602163)
湖北省自然科学基金(2016CFB261)
湖北省教育厅中青年人才项目(Q20161607)
生物质纤维与生态染整湖北省重点实验室开放课题(STRZ201907)资助。
