相转移催化氧化酮羟化反应合成两种甾体药物  

Synthesis of two steroidal drugs by ketohydroxylation catalyzed by phase transfer catalysis

作　　者：冯书晓[1] 齐凯言 王俊岭[1] 马军营[1] 郭亚菲 FENG Shu-xiao;QI Kai-yan;WANG Jun-ling;MA Jun-ying;GUO Ya-fei(College of Chemical Engineering&Pharmaceutical,Henan University of Science and Technology,Luoyang 471023,China)

机构地区：[1]河南科技大学化工与制药学院

出　　处：《化学研究与应用》2020年第2期258-263,共6页Chemical Research and Application

基　　金：河南省自然科学基金资助(182300410353);河南科技大学博士科研启动基金资助(4008/13480055)

摘　　要：以含有17(20)甾体烯烃(1a和2a)为研究对象,对比考察了不同氧化体系以及含有过氧硫酸盐的均相和非均相溶液体系的氧化效果,设计了一种n-Bu4NHSO4/CH2Cl2/H2O相转移催化RuCl3/Oxone氧化酮羟化反应体系,制备得到17α-羟孕酮(1)和醋酸去氧皮质酮(2)两种甾体药物,收率分别达到69%和60%。该双相溶剂体系避免了水和酸性离子对反应的影响,具有步骤简单,副产物少的特点,适用于甾体激素药物α-羟基酮侧链的引入和合成。Two objective substrates(1a and 2a)containing steroidal 17(20)double bonds were compared the oxidation effects in different oxidation systems containing peroxysulfate in homogeneous or heterogeneous solutions.An n-Bu4NHSO4/CH2Cl2/H2O phase transfer catalytic system contain RuCl3/Oxone was designed for ketohydroxylation.17α-hydroxyprogesterone(1)and deoxycorticosterone acetate(2),both steroidal drugs were prepared with yields of 69%and 60%,respectively.The biphasic solvent system avoids disturbed by water and acid,is simple and few by-products,suitable for the introduction ofα-hydroxyketone side chain and synthesize steroid hormone drugs.

关 键 词：甾体药物 相转移催化 氧化酮羟化反应 OXONE α-羟基酮 

分 类 号：O629.23[理学—有机化学] R914.5[理学—化学]