A metal-free and redox-neutral trifluoromethylhydrazination method of alkenes is described. With a commercially available photocatalyst and low-cost reagents, both conjugated and isolated alkenes could be converted to β-trifluoromethyl hydrazines in good to excellent yields. The versatile hydrazine group can be either used for heterocycle synthesis or cleaved to afford a corresponding amine. Mechanistic studies suggested this reaction goes through a radical addition cascade pathway, featuring a fast and irreversible trifluoromethylation and a relatively slow radical hydrazination step.
A visible-light-enabled catalytic intermolecular azido-hydrazination method for unactivated alkenes is developed via an orderly radical addition sequence. This transformation features metal-free and redoxneutral conditions and is applicable to a wide range of alkenes with commercially available reagents. Mechanistic and kinetic studies reveal that the efficient generation of azide radical enabled by fluorenone under visible-light is critical to this methodology. The β-azido alkyl hydrazines prepared with this reaction can be conveniently derived to valuable synthetic building blocks, and one of the products has been successfully applied in the total synthesis of (�)-ibrutinib, which is used to treat B cell cancers.
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