呋喃阿洛糖衍生物水解产物的结构确定  

Structural Elucidation of a Hydrolysis Product from Derivatives of Allofuranose

作　　者：张恩[1] 崔得运 孙伟[1] 李鹏云[1] 徐锦梅[1] 刘宏民[1] ZHANG En;CUI De-yun;SUN Wei;LI Peng-yun;XU Jin-mei;LIU Hong-min(School of Pharmaceutical Science, Zhengzhou University, Zhengzhou 450001, China)

机构地区：[1]郑州大学药学院,河南郑州450001

出　　处：《波谱学杂志》2017年第2期183-190,共8页Chinese Journal of Magnetic Resonance

基　　金：国家自然科学基金资助项目(81172937;U1204206)

摘　　要：1,2;5,6-双-O-异丙叉基-3-C-硝甲基-a-D-呋喃阿洛糖(化合物1)在酸性条件下选择性脱除5,6-异丙叉基得到C-3位构型保持的水解产物1,2-O-异丙叉基-3-C-硝甲基-a-D-呋喃阿洛糖(化合物2);化合物1先经过Moffatt脱水生成C-3硝基烯产物1,2;5,6-双-O-异丙叉基-3-脱氧-亚甲基硝基-a-D-呋喃木糖(化合物3),然后在酸性条件下选择性脱除5,6-异丙叉基过程中协同发生氧杂-Michael加成反应得到C-3位构型反转的水解产物1,2-O-异丙叉基-3-C-硝甲基-a-D-呋喃葡萄糖(化合物2′),两种产物化合物2和2′互为C-3差向异构体.通过~1H NMR、^(13)C NMR、DEPT-135、~1H-~1H COSY、g HSQC和g HMBC等核磁共振(NMR)技术,对化合物2′的~1H和^(13)C NMR数据进行了全归属.1,2-O-(1-methylethylidene)-3-C-methylnitro-?-D-allofuranose(2)was obtained through selective deprotection of1,2;5,6-Di-O-isproplidene-3-C-methylnitro-?-D-allofuranose(1)under an acidic condition.C-3nitrostyrenes(3)was synthetized through Moffatt dehydration from compound1under an acidic condition.A hydrolysis product1,2-O-(1-methylethylidene)-3-C-methylnitro-?-D-glocufuranose(2')which had a reversed C-3configuration was obtained by an unexpected oxa Michael addition.Compounds2and2'were C-3diasteroisomers.Compound2'was characterized with NMR spectroscopy techniques,including1H NMR,13C NMR,DEPT-135,1H-1H COSY,gHSQC and gHMBC.1H and13C chemical shifts of compound2'were also fully assigned.The molecular structure of compound2'was determined.

关 键 词：核磁共振(NMR) 归属 2DNMR 水解产物 

分 类 号：O482.53[理学—固体物理] O621.3[理学—物理]