Research Information System
JOURNAL OF ORGANIC CHEMISTRY, vol.83, pp.8376-8389, 2018 (SCI-Expanded)
An efficient, general, and unprecedented methodology for the synthesis of 2-methylene-2,3-dihydro-1,4-thiazepines from N-propargylic beta-enaminones is described. Initially, N-propargylic beta-enaminones were thionated with Lawesson's reagent in good to high yields, and then the resulting N-propargylic beta-enaminothiones were subjected to electrophilic cyclization. When treated with zinc chloride in refluxing chloroform, Npropargylic beta-enaminothiones underwent electrophilic cyclization to yield 2-methylene-2,3-dihydro-1,4-thiazepines in good to high yields. A general trend was observed for all N-propargylic beta-enaminothiones, and the cyclization proceeded with high efficiency and large functional group tolerance. This process is also applicable to the cyclization of internal alkyne-tethered N-propargylic beta-enaminothiones. This operationally simple and facile method may represent a very rapid entry to a library of functionalized 1,4-thiazepines in the area of pharmaceuticals.