Institute of Next Generation Matter Transformation, College of Chemical Engineering at Huaqiao University, 668 Jimei Blvd, Xiamen, Fujian 361021, P. R. China.
Warshel Institute for Computational Biology, School of Science and Engineering, The Chinese University of Hong Kong, Shenzhen, 2001 Longxiang Road, Shenzhen 518172, P. R. China.
Chem Commun (Camb). 2018 Aug 21;54(65):8960-8963. doi: 10.1039/c8cc04298e. Epub 2018 Jun 22.
An efficient one-pot cascade process via unprecedented quadruple cleavage of BrCFCOOEt with primary amines to afford valuable fluorine-containing heterocycles is described, in which BrCFCOOEt plays a dual role as a C1 synthon and a difluoroalkylating reagent for the first time. Mechanistic studies supported by DFT calculations suggest that a base plays an active role in the formation of the key intermediate isocyanides generated in situ from primary amines and difluorocarbene.
本文首次描述了一种通过 BrCFCOOEt 与伯胺进行前所未有的四重裂解的高效一锅级联过程，以提供有价值的含氟杂环。其中，BrCFCOOEt 首次同时作为 C1 合成子和二氟烷基化试剂发挥作用。通过密度泛函理论（DFT）计算支持的机理研究表明，碱在伯胺原位生成的关键中间体异氰化物的形成中起积极作用。
