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.

Fluorinated alcohols have been widely used in the synthetic organic chemistry over the past decades. The unique properties such as the strong hydrogen‐bonding donor ability and low nucleophilicity allow them to promote organic reactions in the absence of any catalyst. These approaches have distinct advantages in terms of operational simplicity, practicability and environmental friendliness. Reactions promoted by fluorinated alcohols, including nucleophilic substitution reactions, annulation reactions, electrophilic reactions, dearomatization reactions, functionalization of multiple bond, epoxidation reactions and miscellaneous reactions have been summarized in this account.

A one-pot synthesis of phenanthridines and quinolines from commercially available or easily prepared aldehydes has been reported. O-(4-Cyanobenzoyl)hydroxylamine was utilized as the nitrogen source to generate O-acyl oximes in situ with aldehydes catalyzed by Brønsted acid. O-Acyl oximes were then subjected to visible light photoredox catalyzed cyclization via iminyl radicals to furnish aza-arenes. A variety of phenanthridines and quinolines have been prepared assisted by Brønsted acid and photocatalyst under visible light at room temperature with satisfactory yields.

A visible light-induced synthesis of nitrogen-containing arenes from O-2,4-dinitrophenyl oximes has been reported. This photochemical strategy is photocatalyst-free and enabled by electron-donor–acceptor (EDA) complexes of O-2,4-dinitrophenyl oximes and Et3N.

The direct synthesis of nitriles from commercially available or easily prepared aldehydes has been achieved. O-(4-CF3-benzoyl)-hydroxylamine (CF3-BHA) was utilized as the nitrogen source to generate O-acyl oximes in situ with aldehydes, which can be converted to a nitrile with the assistance of a Brønsted acid. Several aliphatic, aromatic, and α,β-unsaturated nitriles that contain different functional groups were prepared in high yields (up to 94% yield). This method has notable advantages, such as simple and mild conditions, high yields, and good functional group tolerance.

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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.

A photocatalytic multi‐component radical relay reaction has been developed for the stereodivergent synthesis of both stereoisomers of α‐aminomethyl cinnamyl ethers. The radical relay reaction of hydroxylamine derivatives, enol ethers and alkenyl boronic acids in DMSO under white LEDs could lead to E‐isomers of α‐aminomethyl cinnamyl ethers. The E‐isomers could subsequently isomerize to less thermodynamically stable Z‐isomers under blue LEDs using toluene as the co‐solvent in a one‐pot manner.