Synthesis of a Central Intermediate in the Biosynthesis of Di- and Trideoxysugars
作者:Thomas Müller、Richard R. Schmidt
DOI:10.1002/jlac.199719970916
日期:1997.9
(6-deoxy-α-D-ribo-hexopyran-3-ulosyl) (2′-deoxythymidin-5′-yl) diphosphate (1) is described. To this end, D-glucose is transformed into known furanose derivative 2 possessing a 3-C-methylene group as latent functionality for 3-ulose generation. From 2, 3,6-dideoxy derivative 6 was synthesized; ensuing acid catalyzed cleavage of the 1,2-O-isopropylidene group and then O-acetylation furnished the required pyranose
二钠的合成(6-脱氧α-D-核糖-hexopyran -3-酮糖基)(2'- deoxythymidin -5'-基)二磷酸(1)进行说明。为此,D-葡萄糖被转化成具有3- C-亚甲基作为潜在的功能性的3-呋喃糖的呋喃糖衍生物2。从2,3,6-双脱氧衍生物6进行合成; 随后通过酸催化裂解1,2- O-异亚丙基,然后进行O-乙酰化,提供了所需的吡喃糖8α,β,可以在异头氧上将其选择性脱乙酰基,得到9α,β。用磷酸化剂13e处理然后氧化生成磷酸二苄基酯衍生物15e,该衍生物可以通过氢解反应进行化学选择脱苄基反应,而不会影响烯烃双键(17);脱-O-乙酰化,然后进行臭氧分解,分别得到未保护的磷酸盐中间体18和19。通过采用核苷磷酸吗啉酸酯方法生成核苷二磷酸糖,两种化合物均可成功用于1的合成。即使在胸腺嘧啶部分的存在下,也可以成功地进行20个烯烃双键的臭氧裂解。