Sund Pernilla, Kronberg Leif
Laboratory of Organic Chemistry, Abo Akademi University, Turku, Abo, Finland.
Nucleosides Nucleotides Nucleic Acids. 2008 Dec;27(12):1215-26. doi: 10.1080/15257770802458162.
The adduct 3-beta-D-ribofuranosyl-3,7,8,9-tetrahydropyrimido[1,2-i]purin-8-ol (2), obtained from adenosine and epichlorohydrin, underwent ring fission at basic conditions. The initial ring-opening took place at C2 of the pyrimidine unit resulting in 2-(5-amino-1-beta-D-ribofuranosyl-imidazol-4-yl)-1,4,5,6-tetrahydropyrimidin-5-ol (3). Also the tetrahydropyrimidine ring of 3 could be opened resulting in 5-amino-1-(beta-D-ribofuranosyl)-imidazole-4-(N-3-amino-2-hydroxyl-propyl)-carboxamide (4). In hot acid conditions, 2 was both deglycosylated and ring-opened yielding 2-(5-amino-imidazol-4-yl)-1,4,5,6-tetrahydropyrimidin-5-ol (7) as the final product. When reacting 3 with CS(2) or HNO(2) ring-closure took place and 3-beta-D-ribofuranosyl-3,4,7,8,9-pentahydropyrimido[1,2-i]purin-8-ol-5-thione (5), and 3-beta-D-ribofuranosyl-imidazo[4,5-e]-3,7,8,9-tetrahydropyrimido[1,2-c][1,2,3]triazine-8-ol (6), respectively, were obtained. Also, the pyrimidine ring of the epichlorohydrin adduct with adenine, 10-imino-5,6-dihydro-4H,10H-pyrimido[1,2,3-cd]purin-5-ol (10), underwent ring fission and the product was identified as 3-hydroxy-1,2,3,4-tetrahydroimidazo[1,5-a]pyrimidine-8-carboximidamide (11).
由腺苷和环氧氯丙烷制得的加合物3-β-D-呋喃核糖基-3,7,8,9-四氢嘧啶并[1,2-i]嘌呤-8-醇（2）在碱性条件下发生开环反应。最初的开环发生在嘧啶单元的C2位，生成2-(5-氨基-1-β-D-呋喃核糖基-咪唑-4-基)-1,4,5,6-四氢嘧啶-5-醇（3）。3的四氢嘧啶环也可以开环，生成5-氨基-1-(β-D-呋喃核糖基)-咪唑-4-(N-3-氨基-2-羟基丙基)-甲酰胺（4）。在热酸条件下，2发生去糖基化和开环反应，最终产物为2-(5-氨基-咪唑-4-基)-1,4,5,6-四氢嘧啶-5-醇（7）。当3与CS(2)或HNO(2)反应时发生闭环反应，分别得到3-β-D-呋喃核糖基-3,4,7,8,9-五氢嘧啶并[1,2-i]嘌呤-8-醇-5-硫酮（5）和3-β-D-呋喃核糖基-咪唑并[4,5-e]-3,7,8,9-四氢嘧啶并[1,2-c][1,2,3]三嗪-8-醇（6）。此外，环氧氯丙烷与腺嘌呤的加合物10-亚氨基-5,6-二氢-4H,10H-嘧啶并[1,2,3-cd]嘌呤-5-醇（10）的嘧啶环也发生开环反应，产物被鉴定为3-羟基-1,2,3,4-四氢咪唑并[1,5-a]嘧啶-8-甲脒（11）。
