核苷第六十七部分：4-氨基-7（8H）蝶啶酮-N8-核苷的合成——腺苷的结构类似物

Nucleosides part LXVI I: synthesis of 4-amino-7(8H)pteridinone-N8-nucleosides-structural analogs of adenosine.

作者信息

Jungmann Oliver, Pfleiderer Wolfgang

机构信息

Fachbereich Chemie, Universitat Konstanz, Postfach, Konstanz, Germany.

出版信息

Nucleosides Nucleotides Nucleic Acids. 2009 May;28(5):550-85. doi: 10.1080/15257770903054241.

DOI:10.1080/15257770903054241

PMID:20183602

Abstract

Various 4-amino-7(8H)pteridones (6, 12, 14, 15, 20, 22) have been glycosylated with 1-chloro-2'-deoxy-D-ribofuranose derivatives (25, 26) applying the new DBU-salt method to form the N(8)-2'-deoxy-D-ribofuranosides (27-36) which can be regarded as 2'-deoxyadenosine analogs. Analogously reacted the 2-N,N-dimethyl-amino-methyleneimino-7(8H)pteridones (43-48) to give preferentially the corresponding N(8)-beta-D-anomers (49-55). Ribosylation with 1-bromo-2,3,5-tri-O-benzoyl-a-D-ribofuranose (56) proceeded as well with 6, 12, 15, 45, and 46 to yield to N(8)-beta-D-ribofuranosides 57-61. Sugar deprotection led to the free N(8)-2'-deoxy-beta-D-ribofuranosides 37-42 and N(8)-beta-D-ribofurano-sides 62-65, respectively. Glycosylations via the silyl-method under Vorbruggen conditions led with 6, 12 and 15 to the same results, however, 4-amino-6-phenyl-7(8H)pteridone (14) reacted differently forming the N(1)-beta-D-ribofuranosides (71, 79) and the N(1)-2'-deoxy-alpha-and ss-D-ribofuranosides 73, 74, 77, 78. The assignments of the structures have been achieved by (1)H-NMR- and UV-spectra. C,H,N-elemental analyses account for the composition.

摘要

采用新的DBU盐法，使各种4-氨基-7(8H)蝶啶酮（6、12、14、15、20、22）与1-氯-2'-脱氧-D-核糖呋喃糖衍生物（25、26）进行糖基化反应，形成可视为2'-脱氧腺苷类似物的N(8)-2'-脱氧-D-核糖呋喃糖苷（27 - 36）。类似地，2-N,N-二甲基-氨基亚甲基亚氨基-7(8H)蝶啶酮（43 - 48）发生反应，优先生成相应的N(8)-β-D-异头物（49 - 55）。6、12、15、45和46与1-溴-2,3,5-三-O-苯甲酰基-α-D-核糖呋喃糖（56）进行核糖基化反应，生成N(8)-β-D-核糖呋喃糖苷57 - 61。糖脱保护分别得到游离的N(8)-2'-脱氧-β-D-核糖呋喃糖苷37 - 42和N(8)-β-D-核糖呋喃糖苷62 - 65。在Vorbruggen条件下，通过硅烷化方法进行的糖基化反应，6、12和15得到相同的结果，然而，4-氨基-6-苯基-7(8H)蝶啶酮（14）反应不同，形成N(1)-β-D-核糖呋喃糖苷（71、79）以及N(1)-2'-脱氧-α-和β-D-核糖呋喃糖苷73、74、77、78。结构的确定通过(1)H-NMR和UV光谱完成。C、H、N元素分析确定了其组成。