Copper-Catalyzed Intermolecular Cross-dehydrogenative C-N Coupling at Room Temperature via Remote Activating Group Enabled Radical Relay Strategy.

Employing -fluorobenzenesulfonimide (NFSI) as a nitrogen-centered radical (NCR) precursor, an intermolecular C(sp)-N coupling on heteroarenes or substituted benzenes with remote activated aniline derivatives via copper catalyzed N-N radical relay strategy at room temperature is developed. Good to excellent yields are acquired, and no ligand or additive is required. Reaction scope investigation and preliminary mechanistic studies demonstrate that the remote activating strategy and delicate control on the reactivities of active NCR species are essential to guarantee satisfactory chemo- and site-selectivity.

Direct Benzylic C(sp)-O Coupling with Alcohol via Site-Selective C(sp)-H Cleavage at Room Temperature through a Remote Directing Group-Enabled Radical Relay Strategy.

Employing a low loading of the terminal oxidant, a remote directing group-enabled radical relay strategy for benzylic direct C(sp)-H alkoxylation with alcohols at room temperature is developed. Satisfactory site-selectivity, chemoselectivity, and reaction scope are achieved under simple and mild conditions, and no ligand or additive is required. Mechanistic studies, ready conversions of the directing group, and other benzylic functionalizations currently under development in our laboratory further indicate the promising potentials of this remote directing group-enabled radical relay strategy.