Novel Synthesis of Anhydronucleosides via the 2′,3′-O-Sulfinate of Purine Nucleosides as Intermediates
Novel Synthesis of Anhydronucleosides via the 2′,3′-O-Sulfinate of Purine Nucleosides as Intermediates
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以嘌呤核苷2′,3′-O-亚磺酸盐为中间体新型合成脱水核苷
DOI：
10.1246/bcsj.48.3243
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发表时间：
1975
影响因子：
4
通讯作者：
K. Tsunoda
中科院分区：
文献类型：
--
作者：
T. Sowa;K. Tsunoda
报道了8，2′-O-anhydro(9-β-D-arabinofuranosyl)-8-hydroxyadenine(3c)和8，2′-S-anhydro(9-β-D-arabinofuranosyl)-8-mercaptoadenine(3a)的合成。活性中间体2‘，3’-O-亚磺基-8-溴腺苷(2a)、2‘，3’-O-亚磺基-8-羟基腺苷(2c)和2‘，3’-O-亚磺基-8-溴鸟苷(2d)是由相应的核苷(1a、1c或1d)在乙腈和水中与亚硫酰氯反应得到的。中间体(2a或2c)在硫脲存在下在正丁醇中加热，或在N，N-二甲基甲酰胺中在乙酸钠存在下加热，以较高的产率生成无水核苷3a和3c。化合物2d环化的所有尝试都失败了。8-巯基腺苷(1b)与亚硫酰氯的反应产物为二(2‘，3’-O-亚磺酰腺苷-8-基)二硫化物(2b)，不能转化为化合物3a。
The synthesis of 8,2′-O-anhydro(9-β-D-arabinofuranosyl)-8-hydroxyadenine (3c) and 8,2′-S-anhydro(9-β-D-arabinofuranosyl)-8-mercaptoadenine (3a) is described. The active intermediates, 2′,3′-O-sulfinyl 8-bromoadenosine (2a), 2′,3′-O-sulfinyl-8-hydroxyadenosine (2c), and 2′,3′-O-sulfinyl-8-bromoguanosine (2d), were prepared from the corresponding nucleosides (1a, 1c or 1d) by successive treatment with thionyl chloride in the presence of pyridine in acetonitrile and with water. The anhydronucleosides, 3a and 3c, were formed in good yields by heating the intermediates (2a or 2c) in n-butanol in the presence of thiourea or in N,N-dimethylformamide in the presence of sodium acetate. All attempts at the cyclization of Compound 2d failed. The reaction product of 8-mercaptoadenosine (1b) with thionyl chloride was identified as the bis(2′,3′-O-sulfinyl adenosin-8-yl) disulfide (2b), which could not be transformed to Compound 3a.