Transition metal-free assembly of 1,3,5-triazines using ethyl bromodifluoroacetate as C1 source

An efficient transition metal-free annulation of amidine with ethyl bromodifluoroacetate to access 2,4-disubstituted-1,3,5-triazines is firstly presented. The desired symmetric and unsymmetric 2,4-disubstituted-1,3,5-triazines were obtained in decent yields via multiple C-N bond formation, in which ethyl bromodifluoroacetate is harnessed as a unique C1 synthon via quadruple cleavage. This reaction is transition metal-free, oxidant-free and simple in operation, and only lowly toxic inorganic wastes are generated.