Transition‐Metal‐Free Olefinic C−H Azidoalkylthiolation via C( sp 3 )−S Bond Cleavage of Vinylsulfonium Salts
Transition‐Metal‐Free Olefinic C−H Azidoalkylthiolation via C( sp 3 )−S Bond Cleavage of Vinylsulfonium Salts
复制标题
通过乙烯基锍盐的 C( sp 3 )-S 键断裂进行过渡-金属-游离烯烃 C-H 叠氮烷基硫基化
DOI：
10.1002/adsc.202200529
复制
发表时间：
2022
影响因子：
5.4
通讯作者：
Zhengkun Yu
中科院分区：
文献类型：
--
作者：
Yuan He;Zilong Huang;Juan Ma;Jie Lin;Yong‐Gui Zhou;Zhengkun Yu
通过叠氮化钠与乙烯基磺酸盐在空气中的C(sp3)−S键裂解，建立了一种无过渡金属的烯烃C−H叠氮烷基硫代化方案。为了实现这一过程，我们开发了一种中断的Pummerer/亲核叠氮烷基化级联反应。通过大规模制备叠氮烷基硫代四取代烯烃产品及其转化为各种三唑和四唑衍生物以及叠氮烷基硫代官能化n杂环化合物，证明了该合成方案的实用性。本合成方法具有底物范围广，在温和条件下具有良好的官能团耐受性的特点。
A transition‐metal‐free olefinic C−H azidoalkylthiolation protocol was developed through C(sp3)−S bond cleavage of vinylsulfonium salts with sodium azide in air under aqueous conditions. An interrupted Pummerer/nucleophilc azidoalkylation cascade was developed for such a process. The practicability of the synthetic protocol was demonstrated by scale‐up preparation of the azidoalkylthiolated tetrasubstituted alkene products and their transformations to diverse triazole and tetrazole derivatives as well as azidoalkylthio‐funtionalizedN‐heterocyclic compounds. The present synthetic methodology features broad substrate scopes and good functional group tolerance under mild conditions.