摘要
以D-核糖为起始原料,用两种不同的方法保护羟基,通过W adsworth-Emmons反应合成1-膦酸二乙酯-D-核糖的α、β端头异构体,以达到优化其合成分离方法的目的。方法A用2,3-O-异丙叉基-5-O-三甲基乙酰基-D-呋喃核糖与四乙基亚甲基二膦酸酯(TEMDP)反应,得到2,3-O-异丙叉基-5-O-三甲基乙酰基-1-亚甲基膦酸二乙酯-D-呋喃核糖,然后用乙醇钠脱去酰基保护基。此时,分离端头异构物,总收率为81%。而后再将α、β分别在酸性条件下水解,得到目的产品,收率分别为94%和91%。方法B则是用2,3,5-O-三苄基-D-呋喃核糖通过W adsworth-Emmons反应形成膦酯糖,分离端头异构体,总收率为70%。然后分别用Pd/C在H2氛条件下还原得目的产物,产率分别为93%和91%。产物用1HNMR表征,证明合成方法可行。
In order to optimize the synthesis and separation of anomers of 1-（diethyl）-2,5-anhydro-D-ribofuranosyl phosphonate, they were synthesized by Wadsworth-Emmons reactions in which two different protected D-ribose derivatives were used as the starting materials. In method A, 2,3-O-isopropylidene-5-O-pivaloyl-D-ribofuranose reacted with tetraethyl methylenediphosphonate （TEMDP） to give 1-（diethyl）-2,3-O-isopropylidene-5-O-pivaloyl-D-ribofuranosyl phosphonate. Sodium ethoxide was used to remove the pivaloyl group in 81% yield. The α and β anomers were isolated and then hydrolyzed under acidic condition to afford the desired products in 94% and 91% yields, respectively. In method B, the D-ribose 1-phosphonates were obtained through the reaction of 2,3,5-tri-O-benzyl-D-ribose with TEMDP in 70% yield. After separating the anomers, the desired products were obtained through deprotection of α and β anomers with Pd/C and H2 in 93% and 91% yields,respectively. The products were characterized by ^1HNMR to verify the feasibility of our synthesis.
出处
《精细化工》
EI
CAS
CSCD
北大核心
2006年第2期157-160,共4页
Fine Chemicals
