Generation of 4′-Carbon Radicals via 1,5-Hydrogen Atom Transfer for the Synthesis of Bridged Nucleosides
Generation of 4′-Carbon Radicals via 1,5-Hydrogen Atom Transfer for the Synthesis of Bridged Nucleosides
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DOI：
10.1021/acs.orglett.2c03285
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发表时间：
2022-10-10
期刊：
影响因子：
5.2
通讯作者：
Hari，Yoshiyuki
中科院分区：
文献类型：
--
作者：
Ito，Yuta;Mizuno，Koichi;Hari，Yoshiyuki
研究了核苷肟酰亚胺经亚胺基诱导的1，5-氢原子转移快速生成4′-碳自由基的方法。4′-碳自由基与烯烃环化，然后亚胺酸酯残基水解，得到各种2′-O，4′-C-和3′-O，4′-C-桥接核苷。该方法操作简单，可用于6′ S-甲基-2 ′-O，4′-C-亚乙基桥连5-甲基尿苷（6′S-Me-ENA-T）和S-限制性乙基桥连5-甲基尿苷（S-cEt-T）的几步合成。
The rapid and facile generation of 4′-carbon radicals from oxime imidates of nucleosides via 1,5-hydrogen atom transfer induced by iminyl radicals was developed. The cyclization of 4′-carbon radicals with olefins, followed by the hydrolysis of imidate residues, provided various 2′-O,4′-C- and 3′-O,4′-C-bridged nucleosides. This operationally simple approach can be applied to the few-step syntheses of 6′S-methyl-2′-O,4′-C-ethylene-bridged 5-methyluridine (6′S-Me-ENA-T) andS-constrained ethyl-bridged 5-methyluridine (S-cEt-T).