School of Chemistry, Trinity Biomedical Sciences Institute (TBSI), Trinity College Dublin, The University of Dublin, Dublin, 2, Ireland.
Chemistry. 2020 Dec 4;26(68):15804-15810. doi: 10.1002/chem.202002542. Epub 2020 Oct 23.
A mild, metal-free, atmospheric oxygen-mediated radical hydrothiolation of alkenes (and alkyne) is reported. A variety of sulfur containing motifs including alkanethiols, thiophenols and thioacids undergo an atmospheric oxygen-mediated radical hydrothiolation reaction with a plethora of alkenes in good yield with excellent functional group compatibility, typically with short reaction times to furnish a range of functionalized products. Biomolecules proved tolerant to the conditions and the procedure is robust and easily executable requiring no specialized equipment. Concise mechanistic studies confirm the process proceeds through radical intermediates in a thiol-ene reaction manifold. The methodology offers an efficient "green" approach for thiol-ene mediated "click" ligation and a milder alternative to thermally initiated hydrothiolation processes.
报道了一种温和、无金属、大气氧介导的自由基氢硫醚化反应，可以用于烯烃（和炔烃）。各种含硫的母体，包括硫醇、硫酚和硫代酸，与大量烯烃在良好的产率下发生大气氧介导的自由基氢硫醚化反应，具有极好的官能团兼容性，通常反应时间短，可得到一系列功能化产物。生物分子对反应条件具有耐受性，该方法具有很强的稳健性，易于操作，不需要特殊设备。简洁的机理研究证实该过程通过硫醇-烯烃反应机理中的自由基中间体进行。该方法为硫醇-烯烃介导的“点击”连接提供了一种有效的“绿色”方法，并且是热引发氢硫醚化过程的温和替代方法。
