Nickel-catalyzed reductive defluorination of iodo allylic gem-difluorides: allenyl monofluoride synthesis
Nickel-catalyzed reductive defluorination of iodo allylic gem-difluorides: allenyl monofluoride synthesis
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镍催化碘代烯丙基偕二氟化物的还原脱氟：丙二烯基一氟化物的合成
DOI：
10.1039/d1cc06457f
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Tao Wu
中科院分区：
文献类型：
--
作者：
Yiming You;Jiayue Wu;Tao Wu
作为一种潜在的氟化合成子，由于对其稳定性的担忧，关于氟化丙二烯的合成和应用的报道非常有限。在这里，我们开发了一种镍催化的碘代烯丙基偕二氟化物的还原脱氟方法，在温和的条件下得到具有良好官能团耐受性的丙二烯基一氟化物，并且很容易转化为其他C-F键化合物，例如烷基氟化物和烯基氟化物。初步机理研究表明，单氟丙二烯是通过将C-I键氧化加成到镍(0)催化剂上，通过β-F消除烯基C-Ni中间体而产生的，而锌使催化剂再生并关闭催化循环。
As a potential fluorinated synthon, there have been only limited reports on fluorinated allene synthesis and applications due to concerns about their stability. Here, we developed a nickel-catalyzed reductive defluorination of iodo allyl gem-difluorides to afford allenyl monofluorides under mild conditions with good functional group tolerance, which were easily converted to other C–F bond compounds, such as alkyl and alkenyl fluorides. Preliminary mechanistic studies suggested that monofluoroallenes were yielded by β-F elimination of the alkenyl C–Ni intermediates from the oxidative addition of C–I bonds to a nickel(0) catalyst, while zinc regenerates the catalyst and closes the catalytic cycle.