Diversity-Oriented Synthesis of Benzo[][1,4]oxazepine-, 2-Chromene-, and 1,2-Dihydroquinoline-Fused Polycyclic Nitrogen Heterocycles under Microwave-Assisted Conditions.

An efficient, diversity-oriented synthesis of oxazepino[5,4-]quinazolin-9-ones, 6-chromeno[4,3-]quinolines, and dibenzo[,][1,6]naphthyridines was established involving a substrate-based approach under microwave-assisted and conventional heating conditions in high yields (up to 88%). The CuBr-catalyzed, chemoselective cascade annulation of -propargylated 2-hydroxybenzaldehydes and 2-aminobenzamides delivered oxazepino[5,4-]quinazolin-9-ones involving a 6-- cyclization-air oxidation-1,3-proton shift-7- cyclization sequence. This one-pot process showed excellent atom economy (-HO) and constructed two new heterocyclic rings (six- and seven-membered) and three new C-N bonds in a single synthetic operation. On the other side of diversification, the reaction between /-propargylated 2-hydroxy/aminobenzaldehydes and 2-aminobenzyl alcohols delivered 6-chromeno[4,3-]quinolines and dibenzo[,][1,6]naphthyridines involving sequential imine formation-[4 + 2] hetero-Diels-Alder reaction-aromatization steps. The influence of microwave assistance was superior to conventional heating, where the reactions were clean, rapid, and completed in 15 min, and the conventional heating required a longer reaction time at a relatively elevated temperature.