Deaminative Allylation of Primary Amines

Nitrogen atoms play pivotal roles in governing molecular properties and biological activity. Accordingly, nitrogen-atom manipulation has emerged as a powerful strategy for skeletal remodeling. However, its integration into classical reactions to redirect their inherent pathways and outcomes remains largely unexplored. Here, we report a deaminative allylation enabled by embedding a photoinduced N-atom deletion process within a classical N-allylation reaction. This reaction-reprogramming strategy transforms ubiquitous alkylamines into α-substituted acrylates and acrylamides-privileged motifs in covalent drugs, chemical biology probes, and functional materials. Mechanistic studies reveal multiple parallel pathways, including deaminative allylation of alkylamines, formal nitrogen-atom deletion of allyl alkylamine intermediates, and denitrogenation of allyl alkyldiazene species, which collectively converge on the same products. The method exhibits broad substrate scope and excellent functional-group tolerance, enabling late-stage modification of natural products and pharmaceuticals. Beyond providing streamlined access to valuable acrylic compounds, this work establishes a pathway-convergent reaction paradigm that harnesses, rather than suppresses, competing reaction pathways, offering new opportunities for bioactive-molecule discovery.