无金属脱氧反应合成抗白血病药物克拉屈滨  

Efficient Synthesis of Cladribine via Metal-free Deoxygenation

作　　者：夏然[1] 孙莉萍[2] 渠桂荣[3] 

机构地区：[1]新乡学院化学化工学院,河南新乡453007 [2]新乡学院生命科学与技术学院,河南新乡453003 [3]河南师范大学化学化工学院,河南新乡453007

出　　处：《化学试剂》2016年第6期511-514,共4页Chemical Reagents

基　　金：国家自然科学基金资助项目(21172059)

摘　　要：报道了无金属催化脱氧反应合成标题化合物的新方法。以2-氯-3',5'-二-O-乙酰基腺苷为原料、乙腈为溶剂,2'-羟基和苯氧基硫代酰氯反应,继而以(Bu4N)2S2O8和HCO2Na为非金属脱氧试剂,代替文献报道的Bu3Sn H/AIBN体系,以DMF为溶剂,80℃反应4 h,以82%收率得到脱氧中间体。脱氧中间体在Na2CO3/CH3OH体系中脱除乙酰基。经3步反应以66.3%总收率得到克拉屈滨。该方法高效、简便,不用柱层析,易于操作,为克拉屈滨的制备提供了有效途径。The synthesis of anti-leukemia drug Cladribine via the metal-free deoxygenation was developed.In acetonitril,2＇-hydroxyl group of 2-chloro-3＇,5＇-di-O-acetyladenosine was esterificated with phenyl thioxochloroformate.The esterificated nucleoside was deoxygenated at 80 ℃ for 4 h using（Bu4N）2S2O8and HCO2 Na instead of Bu3 Sn H/AIBN as deoxygenation system,and cladribine could be obtained in 66.3% total yield after the de-acetylation in Na2CO3/CH3 OH system.The intermediates and product could be purified by simple work-up process and chromatography was avoided,which made this route more attractive for industrial applications.

关 键 词：克拉屈滨 无金属催化 脱氧 核苷合成 

分 类 号：O629.3[理学—有机化学]