In this work, we have described an alternative alkenylation approach to illustrate the metal-like behaviour of iodine in cross-coupling reactions. Alkenylation could proceed through iodide catalysed radical initiation, radical addition and iodine promoted alkenyl functionality recovery. Catalytic HI elimination similar to the β-hydride elimination of transition metals was realized for the radical alkenylation of sulfonyl hydrazides. Operando IR and cyclic voltammetry experiments were carried out to confirm the crucial role of iodine in the radical alkenylation process.

A palladium-catalyzed reaction of primary amines with iodoarenes produces γ-arylated primary amines. A bulky salicylaldehyde, which is marked as easily available, installable, removable, and recoverable, plays a key role in directing palladium to site-selectively activate the C-H bond located γ to the amino group.

By combining catalytic nucleophilic enamine activation with Pd-catalyzed C-H activation of allylarenes, the first oxidative allylic alkylation of unactivated ketones was achieved. Mechanistically, the Pd-catalyzed allylic C-H activation and proline-catalyzed ketone nucleophilic activation worked synergistically for the oxidative cross-coupling between allylarenes and unactivated ketones.

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