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The use of methyl 2,2-difluoro-2-(fluorosulfonyl)acetate as the difluorocarbene source to generate an in situ source of difluoromethylene triphenylphosphonium ylide
Journal of Fluorine Chemistry ( IF 1.7 ) Pub Date : 2013-03-13 , DOI: 10.1016/j.jfluchem.2013.02.026
Charles S. Thomoson , Henry Martinez , William R. Dolbier

Under moderate conditions in the presence of a demethylating reagent, such as iodide, methyl 2,2,-difluoro-2-(fluorosulfonyl)acetate (MDFA) releases difluorocarbene, which in the presence of triphenylphosphine forms difluoromethylene triphenylphosphonium ylide. When the process is carried out also in the presence of aldehydes or activated ketones, the ensuing in situ Wittig-type reaction of the ylide with the carbonyl reactants produces 1,1-difluoroalkenes in good yield. Density Functional Theory calculations were used to provide new estimates of the energies and structures of singlet and triplet states of CH2:, CHF:, and CF2: carbenes, as well as those of their respective triphenylphosphonium ylides.



中文翻译:

使用2,2-二氟-2-(氟磺酰基)乙酸甲酯作为二氟卡宾源以原位生成二氟亚甲基三苯基叶立德源

在中等条件下,在诸如碘化物之类的去甲基化试剂的存在下,2,2,-二氟-2-(氟磺酰基)乙酸甲酯(MDFA)释放出二氟卡宾,其在三苯基膦的存在下形成二氟亚甲基三苯基phosph叶立德。当该方法是在醛或酮活化的存在也进行,在与羰基的反应物的内鎓盐的维悌希原位型反应随后产生良好产率1,1- difluoroalkenes。密度泛函理论计算被用来提供能量和CH的单线态和三态的结构,新的估计2:,CHF:和CF 2:卡宾,以及那些各自的三苯基膦叶立德。

更新日期:2013-03-13
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