| Abstract: | The Mukaiyama–Michael‐type addition of various silyl ketene acetals or silyl enol ethers on some 1,2‐diaza‐1,3‐butadienes proceeds at room temperature in the presence of catalytic amounts of Lewis acid affording by heterocyclization 1‐aminopyrrol‐2‐ones and 1‐aminopyrroles, respectively. 1‐Aminoindoles have been also obtained by the same addition of 2‐(trimethylsilyloxy)‐1,3‐cyclohexadiene on some 1,2‐diaza‐1,3‐butadienes and subsequent aromatization. Mechanistic investigations indicate the coordination by Lewis acid of the enolsilyl derivative and its 1,4‐addition on the azo‐ene system of 1,2‐diaza‐1,3‐butadienes. The migration of the silyl group from a hydrazonic to an amidic nitrogen, its acidic cleavage and the final internal heterocyclization give the final products. Based on NMR studies and ab initio calculations, a plausible explanation for the migration of the silyl protecting group is presented. |
