The Williams group has recently reported several highly-strained azahomocubanes such as 1-azahomocubane.1 The synthesis of the 5-azatriblattane skeleton, a seco-5-azahomocubane, used the Diels-Alder reaction of 2-azetines and cyclopentadiene as the key step in constructing the caged core.2 While further exploring the cycloaddition reactivity of the 2-azetine system, this unsaturated 4-membered heterocycle was found to undergo electrocyclic ring-opening to give N-substituted 1-azabutadienes. These nitrogenous analogues of butadiene have received much less study than their carbon counterpart, largely due to their instability, inaccessibility, and reactivity. Microwave irradiation at 110°C proved sufficient to generate these highly reactive dienes, which had only been obtained by flash vacuum pyrolysis previously (<300°C).3 This talk shares the details of the discovery, observation of the intermediate azabutadiene, explores the tolerance of various N-protecting groups to this process, and investigates subsequent Diels-Alder reaction of intermediate azabutadienes with various dienophiles. Cycloaddition between the highly reactive azadiene intermediates and their parent systems gave hitherto unreported bicycles. Chemoreactivity of the intermediate N-acyl-1-azabutadiene trienes was strongly influenced by protecting group, affording both dihydro-1,3,-oxazines and tetrahydropyridines. Synthetically interesting aldehydes and tetrahydropyridones were obtained upon hydrolysis of obtained cycloadducts.