Serendipitous One-Step Synthesis of Cyclopentene Derivatives from 5′-Deoxy-5′-heteroarylsulfonylnucleosides as Nucleoside-Derived Julia-Kocienski Reagents
Serendipitous One-Step Synthesis of Cyclopentene Derivatives from 5′-Deoxy-5′-heteroarylsulfonylnucleosides as Nucleoside-Derived Julia-Kocienski Reagents
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DOI：
10.1021/acs.joc.1c01940
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发表时间：
2021-12-03
影响因子：
3.6
通讯作者：
Ando，Kaori
中科院分区：
文献类型：
--
作者：
Oka，Natsuhisa;Kanda，Mayuka;Ando，Kaori
报道了5′-脱氧-5 ′-杂芳基磺酰基核苷一步合成环戊烯衍生物的方法。这种独特的转化可能通过由杂芳基砜的α-去质子化引发的多米诺反应和随后的消除反应进行，以生成核碱基和含有甲酰基的α，β-不饱和砜。核碱基与α，β-不饱和砜的迈克尔加成和随后的分子内Julia-Kocienski反应最终产生环戊烯环。通过分别在杂芳基硫醇和硫代羧酸的存在下进行该反应，杂芳硫基和酰基硫基可以取代核碱基掺入环戊烯核中。顺式，顺式-三取代的环戊烯衍生物作为单一立体异构体从核糖核苷衍生的Julia-Kocienski砜获得。
A serendipitous one-step transformation of 5′-deoxy-5′-heteroarylsulfonylnucleosides into cyclopentene derivatives is reported. This unique transformation likely proceeds via a domino reaction initiated by α-deprotonation of the heteroaryl sulfone and subsequent elimination reaction to generate a nucleobase and an α,β-unsaturated sulfone that contains a formyl group. The Michael addition of the nucleobase to the α,β-unsaturated sulfone and the subsequent intramolecular Julia–Kocienski reaction eventually generate the cyclopentene ring. Heteroarylthio and acylthio groups can be incorporated into the cyclopentene core in place of the nucleobase by conducting this reaction in the presence of a heteroarylthiol and a thiocarboxylic acid, respectively.cis,cis-Trisubstituted cyclopentene derivatives are obtained as a single stereoisomer from ribonucleoside-derived Julia–Kocienski sulfones.