Planas Ferran, Kohlhepp Stefanie V, Huang Genping, Mendoza Abraham, Himo Fahmi
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, 10691, Stockholm, Sweden.
Department of Chemistry, School of Science, Tianjin University, Tianjin, 300072, P. R. China.
Chemistry. 2021 Feb 5;27(8):2767-2773. doi: 10.1002/chem.202004164. Epub 2021 Jan 12.
The dynamic equilibria of organomagnesium reagents are known to be very complex, and the relative reactivity of their components is poorly understood. Herein, a combination of DFT calculations and kinetic experiments is employed to investigate the detailed reaction mechanism of the Pummerer coupling between sulfoxides and turbo-organomagnesium amides. Among the various aggregates studied, unprecedented heterometallic open cubane structures are demonstrated to yield favorable barriers through a concerted anion-anion coupling/ S-O cleavage step. Beyond a structural curiosity, these results introduce open cubane organometallics as key reactive intermediates in turbo-organomagnesium amide mixtures.
有机镁试剂的动态平衡非常复杂，人们对其各组分的相对反应性了解甚少。在此，采用密度泛函理论（DFT）计算和动力学实验相结合的方法，研究亚砜与超有机镁酰胺之间普默勒尔偶联反应的详细机理。在研究的各种聚集体中，前所未有的异金属开放立方烷结构通过协同的阴离子-阴离子偶联/S-O裂解步骤产生了有利的势垒。除了结构上的新奇之处，这些结果表明开放立方烷有机金属化合物是超有机镁酰胺混合物中的关键反应中间体。
