With support from the Chemical Mechanism, Function, and Properties Program in the Division of Chemistry, a research team at the University of Illinois at Chicago are developing new reactions to rapidly assemble novel molecules through unconventional strategies using N-alkenylnitrones and N,O-dialkenylhydroxylamines as reactive intermediates. The rearrangement reactivity of these intermediates is being controlled to form more complex molecules with defined three-dimensional structure. Simple modular routes to generate N-alkenylnitrones and N,O-dialkenylhydroxylamines from readily available reagents are being used to facilitate these activities. This work is targeting improved synthetic efficiency to expand chemical space. Improvements in this area are necessary to support the discovery, accessibility, and study of biologically active molecules, as well as the development of new materials. These activities are also providing training for graduate and undergraduate students to become successful members of the chemical workforce and lowering barriers to students engaging in undergraduate research and considering chemistry career paths. Improving efficiency to enable rapid access to new molecular targets and expanding chemical space to include new molecular architectures remain two critical needs in organic synthesis to support demands for new compounds with novel properties for medicinal and material applications. The unique reactivity of N-alkenylnitrones and N,O-dialkenylhyd