Li Hengyuan, Qin Linqian, Nie Jia, Jiang Huanfeng, Zhu Chuanle
School of Chemistry and Chemical Engineering, Key Laboratory of Functional Molecular Engineering of Guangdong Province, South China University of Technology, Guangzhou 510640, China.
Pazhou Lab, Guangzhou 510335, China.
Org Lett. 2023 Jul 28;25(29):5431-5436. doi: 10.1021/acs.orglett.3c01713. Epub 2023 Jun 26.
For over half a century, by activation of alcohols with activators, deoxygenative substitution of alcohols has been limited to employing nucleophiles with a single nucleophilic site. Herein, we demonstrate a fluoroolefin-mediated deoxygenative substitution of nonactivated and activated alcohols with diverse acidic nucleophiles, with inversion of configuration, to allow chemo- and enantiospecific construction of C-S, C-N, C-O, and C-Se bonds by the distinction of the different nucleophilic sites of the nucleophiles. The formed -tethered monofluoroalkene was the intermediate.
半个多世纪以来，通过用活化剂活化醇类，醇的脱氧取代反应一直局限于使用具有单个亲核位点的亲核试剂。在此，我们展示了一种氟代烯烃介导的未活化和活化醇与多种酸性亲核试剂的脱氧取代反应，构型发生翻转，通过区分亲核试剂的不同亲核位点，实现C-S、C-N、C-O和C-Se键的化学和对映体特异性构建。所形成的连接单氟烯烃为中间体。
