Promoted　by　K2CO3　(2.0　equiv),　the　1,3-dipolar　[3+3]　cycloaddition　between　1,　4-benzodiazepinone-based　nitrones　and　alpha-halohydroxamates　processed　smoothly　under　the　mild　reaction　conditions　and　delivered　structurally　novel　and　complex　cis-　or　trans-configured　d-edge　heterocycle-fused　1,4-benzodiazepinones　in　up　to　＞99%　isolated　yield　with　＞20:1　dr.　The　relative　configuration　of　the　title　chemical　entities　was　clearly　identified　with　the　use　of　single-crystal　X-ray　structure　analysis.　The　reaction　mechanism　was　assumed　to　interpret　the　diastereoselective　production　of　the　obtained　cis-　or　trans-configured　d-edge　heterocycle-fused　1,4-benzodiazepinones.