A unified strategy involving visible-light-induced iminyl-radical formation has been established for the construction of pyridines, quinolines, and phenanthridines from acyl oximes. With fac-[Ir(ppy)3 ] as a photoredox catalyst, the acyl oximes were converted by 1 e(-) reduction into iminyl radical intermediates, which then underwent intramolecular homolytic aromatic substitution (HAS) to give the N-containing arenes. These reactions proceeded with a broad range of substrates at room temperature in high yield. This strategy of visible-light-induced iminyl-radical formation was successfully applied to a five-step concise synthesis of benzo[c]phenanthridine alkaloids.

Aunified strategy involving visible-lightinduced iminyl-radical formation has been established for the construction of pyridines,quinolines, and phenanthridines from acyl oximes.W ithf ac-[Ir(ppy) 3 ]asaphotoredox catalyst, the acyl oximes were converted by 1e À reduction into iminyl radical intermediates,w hich then underwent intramolecular homolytic aromatic substitution (HAS) to give the N-containing arenes.These reactions proceeded with ab road range of substrates at room temperature in high yield. This strategy of visible-lightinduced iminyl-radical formation was successfully applied to afive-step concise synthesis of benzo[c]phenanthridine alkaloids.Scheme1. N À Oc leavage of acyl oximes to form N-containing heterocycles. MW = microwave radiation.

Ar egiospecific synthesis of orthotrifluoromethylated and ortho-(fluoro)alkylated pyridine derivatives has been developed. This strategy is enabled by visiblel ight-promoted vinyl isocyanide insertions with Umemotos reagent and electron-deficient bromides at room temperature.T he methodologyp resentedh ere provides an access to highly functionalized ortho-(fluoro)alkylated pyridine derivatives regiospecifically under mild conditions with good yields.T he proposedm echanism was supported by TEMPO trappinge xperiments, Stern-Volmer analysis andl ight off/on andt ime profile experiments.

We report a diastereoconvergent synthesis of anti-1,2-amino alcohols bearing N-containing quaternary stereocenters using an intermolecular direct C-H amination of homoallylic alcohol derivatives catalyzed by a phosphine selenide. Destruction of the...

Phosphine selenides are introduced as an alternate class of selenium-based catalysts for the aza-Heck reaction of alkenes. Using these catalysts, a range of terminal alkenes react with NFBS to give oxidative amination products. Judicious choice of phosphine ligand gives greater regio-and stereoselectivity than with diphenyl diselenide, enabling the selective formation of E terminal enimides in high yields. Isotope-labeling experiments and measurements of kinetic isotope effects reveal that the reaction occurs stereospecifically via irreversible anti addition, followed by rate-determining syn elimination.