Darù Andrea, Hu Xile, Harvey Jeremy N
Department of Chemistry, Division of Quantum Chemistry and Physical Chemistry, KU Leuven, Celestijnenlaan 200F, 3001 Heverlee, Belgium.
Laboratory of Inorganic Synthesis and Catalysis, Institute of Chemical Sciences and Engineering, École Polytechnique FÉdÉrale de Lausanne (EPFL), ISIC-LSCI, BCH 3305, Lausanne 1015, Switzerland.
ACS Omega. 2020 Jan 15;5(3):1586-1594. doi: 10.1021/acsomega.9b03578. eCollection 2020 Jan 28.
In a recent study, a new procedure for -selective olefin synthesis by reductive coupling of alkyl iodides with terminal alkynes in the presence of iron salts is described. This transformation is representative of many newly developed synthetic routes through the involvement of multiple species and phases, which makes mechanistic insight hard to obtain. Here, we report computational work aimed at exploring the possible reaction pathways. DFT calculations lead to two suggested routes, one involving C-I reduction by metallic zinc and radical addition to the alkyne and the other involving addition of two reduced iron species to the alkyne bond followed by reductive elimination. Comparison to experimental results as well as kinetic modeling is used to discuss the likelihood of these and related mechanisms.
在最近的一项研究中，描述了一种在铁盐存在下通过烷基碘与末端炔烃的还原偶联进行 - 选择性烯烃合成的新方法。这种转化是许多新开发的合成路线的代表，这些路线涉及多种物种和相，这使得难以获得机理见解。在这里，我们报告了旨在探索可能反应途径的计算工作。密度泛函理论（DFT）计算得出了两条建议路线，一条涉及金属锌对C-I的还原以及自由基对炔烃的加成，另一条涉及两个还原态铁物种对炔烃键的加成，随后进行还原消除。通过与实验结果以及动力学建模进行比较，来讨论这些及相关机理的可能性。
