4-氨基嘧啶核苷化反应中 Dimroth 重排的意外观察。
Unexpected Observation of the Dimroth Rearrangement in the Ribosylation of 4-Aminopyrimidines.
机构信息
PTC Therapeutics, Inc. , 100 Corporate Ct., South Plainfield, New Jersey 07080, United States.
出版信息
J Org Chem. 2017 Jun 2;82(11):5881-5889. doi: 10.1021/acs.joc.7b00780. Epub 2017 May 23.
A method for the preparation of 1-(N-ribofuranosyl)-6-imino-1,6-dihydropyrimidin-4-amines 3 or 4-(N-ribofuranosyl)-6-aminopyrimidines 4 via glycosylation of 4-aminopyrimidines 2 or 5 is described. Silylated 4-aminopyrimidines 2 or 5 upon ribosylation with 1 provide products 3. When intermediates 3 contain a strongly electron-withdrawing group, such as C(4)-Cl or C(5)-NO, they rearrange to products 4 in the presence of aqueous ammonia. A mechanism is proposed that involves a ring-opening/ring-closing (Dimroth) rearrangement.
通过 4-氨基嘧啶 2 或 5 的糖基化，描述了 1-(N-呋喃核糖基)-6-亚氨基-1,6-二氢嘧啶-4-胺 3 或 4-(N-呋喃核糖基)-6-氨基嘧啶 4 的制备方法。用 1 对硅烷基化的 4-氨基嘧啶 2 或 5 进行核糖基化可得到产物 3。当中间体 3 含有强吸电子基团，如 C(4)-Cl 或 C(5)-NO 时，它们在氨水溶液中会重排为产物 4。提出了一个涉及开环/闭环（Dimroth）重排的机制。
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