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Abstract
<jats:p>Transition-metal-catalyzed cross-coupling has long enabled efficient C–C bond formation through polar bond disconnections, yet the increasing saturation and structural complexity of contemporary molecular architectures have exposed limitations in scope and functional-group compatibility. Radical cross-coupling (RCC) has emerged as a powerful alternative, allowing the direct use of abundant functional groups under mild conditions, but it has typically relied on external redox activation that introduces additional complexity and often limits operational simplicity and scalability. Redox-neutral RCC with alkyl sulfonyl hydrazides represents a conceptually distinct approach that eliminates the need for exogenous oxidants or reductants while preserving, and in many cases extending, the breadth of radical reactivity. Alkyl sulfonyl hydrazides are versatile radical precursors that serve the dual role of radical source and internal electron donor, this platform combines the operational simplicity of classical two-electron couplings with the functional-group tolerance of single-electron chemistry. In this Perspective we examine the mechanistic foundations of these transformations, highlight emerging applications in synthesis and medicinal chemistry, and outline the key challenges as this method evolves into a general and predictive paradigm for bond construction.</jats:p>