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.
Modification of photocatalyst reactivity through intermolecular
interactions represents a straightforward and convenient strategy
for catalyst designation. Herein, we reported that upon the addition
of B(C6F5)3·H2O,
the oxidation potential of quinoxalinone increased remarkably, enabling
the photoredox aerobic oxidation of alcohol, thiols, and alkenes toward
carbonyl compounds and dithioethers under visible light conditions.
Mechanistic studies, including X-ray structure analysis, cyclic voltammetry,
electron paramagnetic resonance measurements, UV–vis absorption,
and fluorescence spectra, revealed that the quinoxalinone–B(C6F5)3·H2O combo could
serve as a versatile photocatalyst for both energy transfer and single
electron transfer processes.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.