Synthesis of 1‐azacycl[3.2.2]azine and 1‐azabenzo[h]cycl[3.2.2]azine

Abstract 1‐Azacycl[3.2.2]azines were synthesized from 2‐methylthioimidazo[1,2‐a]pyridines, 2a and 2b, by using [2 + 8] cycloaddition reaction with dimethyl acetylenedicarboxylate as the key step. Synthesis of 1‐azabenzo‐[h]cycl[3.2.2]azine was also described.