通过Michael加成引发分子间的环丙烷化反应高效合成螺环嘧啶核苷（英文）  

Efficient Synthesis of Spirocyclic Nucleosides via Michael Addition-Initiated Intermolecular Cyclopropanation Reaction

作　　者：郝二军 张庆 张齐英 渠桂荣 杨西宁 郭海明 Hao Eijun;Zhang Qing;Zhang Qiying;Qu Guirong;Yang Xining;Guo Haiming(Henan Key Laboratory of Organic Functional Molecules and Drug Innovation,Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals,School of Chemistry and Chemical Engineering,Henan Normal University,Xinxiang,Henan 453007;Xinxiang Tuoxin Pharmaceutical Co.,Ltd.,Xinxiang,Henan 453000)

机构地区：[1]河南师范大学化学化工学院,精细化学品绿色制造河南省协同创新中心,河南省有机功能分子与药物创新重点实验室,河南新乡453007 [2]新乡拓新药业股份有限公司,河南新乡453000

出　　处：《有机化学》2019年第11期3237-3243,共7页Chinese Journal of Organic Chemistry

基　　金：Project supported by the National Natural Science Foundation of China(Nos.21602045,U1604283);the Henan Postdoctoral Science Foundation Funded Project(No.2015071);Overseas Expertise Introduction Project for Discipline Innovation(111 Project,No.D17007)~~

摘　　要：报道了一种简单高效的螺环核苷合成方法,以α-嘧啶取代的丙烯酸酯和α-氯代环烷酮为原料, KO^tBu为碱,通过Michael加成引发的环丙烷化反应,高效合成一系列2?-螺环修饰的三元碳环嘧啶核苷.该反应底物适用范围较宽,非对映选择性较高(>20:1 dr),收率可高达85%.An efficient route to synthesize 2’-spiro[2-oxocyclopentyl]cyclopropyl nucleoside analogues via KO^tBu promoted Michael addition-initiated cyclopropanation reactions of α-thymine acrylates with α-chloro-cycloalkanones has been developed. A wide range of C(2′)-spirocyclic modified nucleoside analogues were obtained with excellent diastereoselectivities(>20:1) and good yields(up to 85%).

关 键 词：螺环核苷 环丙烷化反应 α-氯代环烷酮 

分 类 号：O62[理学—有机化学]