9-(5-脱氧-β-赤式-戊-4-烯呋喃糖基)腺嘌呤的对映体形式及5-脱氧-D-来苏糖的一种新制备方法。

Enantiomeric forms of 9-(5-deoxy-beta-erythro-pent-4-enofuranosyl)adenine and a new preparation of 5-deoxy-D-lyxose.

作者信息

Lerner L M

出版信息

Carbohydr Res. 1977 Feb;53(2):177-85. doi: 10.1016/s0008-6215(00)88085-4.

Abstract

Methyl 5-deoxy-5-iodo-2,3-O-isopropylidene-beta-D-ribofuranoside (3) was obtained in three steps from D-ribose. Exchange of the isopropylidene group for benzoate groups and acetolysis gave 1-O-acetyl-2,3-di-O-benzoyl-5-deoxy-5-iodo-D-ribofuranose which was coupled with 6-benzamidochloromercuripurine by the titanium tetrachloride method to afford the blocked nucleoside. Treatment with 1,5-diazabicyclo[5.4.0]undec-5-ene in N,N-dimethylformamide and removal of the blocking groups have 9-(5-deoxy-beta-D-erythro-pent-4-enofuranosyl)adenine (9). A similar route starting from methyl 5-deoxy-5-iodo-2,3-O-isopropylidene-alpha-D-lyxofuranoside (14) afforded the enantiomeric nucleoside, 9-(5-deoxy-beta-L-erythro-pent-4-enofuranosyl)adenine (20). Methyl 2,3-O-isopropylidene-alpha-D-mannofuranoside was treated with sodium periodate and then with sodium borohydride to give methyl 2,3-O-isopropylidene-alpha-D-lyxofuranoside (11). Acid hydrolysis afforded D-lyxose. Tosylation of 11 gave methyl 2,3-O-isopropylidene-5-O-p-tolylsulfonyl-alpha dp-lyxofuranoside (12) which was converted into 14 with sodium iodide in acetone. Reduction of 12 gave methyl 5-deoxy-2,3-O-isopropylidene-alpha-D-lyxofuranoside which was hydrolyzed to give 5-deoxy-D-lyxose.

摘要

5-脱氧-5-碘-2,3-O-异亚丙基-β-D-呋喃核糖苷（3）由D-核糖经三步反应制得。将异亚丙基换成苯甲酸酯基并进行乙酰解反应，得到1-O-乙酰基-2,3-二-O-苯甲酰基-5-脱氧-5-碘-D-呋喃核糖，它通过四氯化钛法与6-苯甲酰胺基氯汞嘌呤偶联，得到保护核苷。在N，N-二甲基甲酰胺中用1,5-二氮杂双环[5.4.0]十一碳-5-烯处理并脱去保护基，得到9-(5-脱氧-β-D-赤式-戊-4-烯呋喃糖基)腺嘌呤（9）。从5-脱氧-5-碘-2,3-O-异亚丙基-α-D-来苏呋喃糖苷（14）出发，经类似路线得到对映体核苷9-(5-脱氧-β-L-赤式-戊-4-烯呋喃糖基)腺嘌呤（20）。2,3-O-异亚丙基-α-D-甘露呋喃糖苷先用高碘酸钠处理，再用硼氢化钠处理，得到2,3-O-异亚丙基-α-D-来苏呋喃糖苷（11）。酸水解得到D-来苏糖。11经甲苯磺酰化得到2,3-O-异亚丙基-5-O-对甲苯磺酰基-α-D-来苏呋喃糖苷（12），它在丙酮中用碘化钠转化为14。12还原得到5-脱氧-2,3-O-异亚丙基-α-D-来苏呋喃糖苷，水解得到5-脱氧-D-来苏糖。