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ChemRxivBoryl Radical beta-Scission Enables Divergent Deaminative Cross-Coupling of AminesAmines are among the most common functional groups in bioactive molecules and pharmaceuticals, yet they are almost universally treated as synthetic endpoints. Here we report a strategy that repositions native primary, secondary, and tertiary amines as versatile handles for divergent cross-coupling. The platform relies on in situ activation via borane coordination and exploits a copper catalytic redox system that generates amine-ligated boryl radicals, which undergo beta-scission across the C(sp³)–N bond to release alkyl radicals. These intermediates engage in copper-catalyzed cross-couplings with a broad array of C-, N-, O-, and S-based nucleophiles. The method tolerates diverse amine classes, enables modular functionalization, and supports late-stage editing of complex drug scaffolds. In addition, amides can be incorporated into the manifold via reductive funneling. This work establishes a general approach to deaminative C–N bond functionalization and introduces a new logic for retrosynthetic diversification and pharmacophore remodeling.