核酸相关化合物。118. 氨基嘌呤衍生物的非水重氮化反应。通过酰卤或硅卤化物方便地合成6-卤代和2,6-二卤代嘌呤核苷及2'-脱氧核苷。
Nucleic acid related compounds. 118. Nonaqueous diazotization of aminopurine derivatives. Convenient access to 6-halo- and 2,6-dihalopurine nucleosides and 2'-deoxynucleosides with acyl or silyl halides.
作者信息
Francom Paula, Robins Morris J
机构信息
Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602-5700, USA.
出版信息
J Org Chem. 2003 Jan 24;68(2):666-9. doi: 10.1021/jo020625a.
Treatment of 9-(2,3,5-tri-O-acetyl-beta-d-ribofuranosyl)-2-amino-6-chloropurine (1) with TMS-Cl and benzyltriethylammonium nitrite (BTEA-NO2) in dichloromethane gave the crystalline 2,6-dichloropurine nucleoside 2, and acetyl chloride/BTEA-NO2 was equally effective ( approximately 85%, without chromatography). TMS-Br/tert-butyl nitrite/dibromomethane gave crystalline 2-bromo-6-chloro analogue 3 (85%). (Chloro or bromo)-dediazoniation of 3',5'-di-O-acetyl-2'-deoxyadenosine (4) gave the 6-[chloro (5, 63%) or bromo (6, 80%)]purine deoxynucleosides, and 2',3',5'-tri-O-acetyladenosine (8) was converted into the 6-chloropurine nucleoside 9 (71%).
在二氯甲烷中，用三甲基氯硅烷（TMS-Cl）和苄基三乙基氯化铵亚硝酸酯（BTEA-NO₂）处理9-(2,3,5-三-O-乙酰基-β-D-呋喃核糖基)-2-氨基-6-氯嘌呤（1），得到结晶状的2,6-二氯嘌呤核苷2，乙酰氯/BTEA-NO₂同样有效（约85%，无需色谱分离）。三甲基溴硅烷/叔丁基亚硝酸酯/二溴甲烷得到结晶状的2-溴-6-氯类似物3（85%）。3',5'-二-O-乙酰基-2'-脱氧腺苷（4）的（氯或溴）脱重氮化反应得到6-[氯（5，63%）或溴（6，80%）]嘌呤脱氧核苷，并且2',3',5'-三-O-乙酰基腺苷（8）转化为6-氯嘌呤核苷9（71%）。
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