Radical-mediated　reactions　have　many　advantages　in　the　construction　of　complex　molecular　scaffolds　by　forging　chemical　bonds　of　high　challenge.　Diazenes,　including　1,1-diazenes　and　1,2-diazenes,　can　generate　biradical　species　via　nitrogen　extrusion　under　thermal　or　photochemical　conditions.　The　superior　reactivity　of　the　generated　biradical　enables　various　types　of　synthetic　transformations　with　excellent　chemoselectivity　and　has　been　applied　to　the　complex　natural　products　synthesis.　In　this　mini-review,　the　modes　of　reaction　are　summarized　and　discussed,　namely　ring　contraction　via　nitrogen　deletion,　homo　or　hetero-dimerization,　trimethylenemethane　(TMM)-diyl　cycloaddition.　Applications　of　these　classes　of　reactions　in　complex　natural　product　synthesis　are　illustrated.　Last　but　not　least,　the　current　state,　future　directions,　and　opportunities　for　dinitrogen　extrusion　reaction　from　diazenes　are　highlighted　and　discussed.　©　2022