On account of the broad utilities of organophosphorus compounds, the development of highly efficient and concise phosphination methods is significantly important and urgent. Herein, we disclose a novel method for the synthesis of phosphorylated heterocycles: versatile intermediate propargylamines serving as a new type of radical acceptors incorporated in P-radicals via a photocatalytic strategy. This reaction proceeds through a cascade phosphinoylation/cyclization/oxidation/aromatization pathway using readily available starting materials under mild conditions of light with excellent atom economy, catalyzed by AgOAc or fac-Ir(ppy)3. One of the phosphorylated quinolines was selected, as an example, as an electron-transporting material for fabricating phosphorescence organic light-emitting diodes displaying excellent electroluminescence performances with a maximum external quantum efficiency of 21.9% with negligible efficiency roll-off ratios.

Three phosphoryl quinoline derivatives, (2,4-diphenylquinolin-3-yl)diphenylphosphine oxide (QDPO), (2,4-diphenylbenzo[h]quinolin-3-yl)diphenylphosphine oxide (B-QDPO) and (2-([1,1′-biphenyl]-4-yl)-4-phenylquinolin-3-yl)diphenylphosphine oxide (BP-QDPO), comprising two electron-transporting moieties namely a nitrogen heterocycle and a phosphoryl (PO) group, have been designed and synthesized. All materials exhibit suitable LUMO (lowest unoccupied molecular orbital)/HOMO (highest occupied molecular orbital) levels, large triplet energy gaps (ET > 3.1 eV) and excellent thermal stabilities. These materials were utilized as electron transporting materials for fabricating green phosphorescent organic light-emitting diodes with the configuration of indium tin oxide (ITO)/MoO3 (5 nm)/TAPC (di-[4-(N,N-ditolyl-amino)-phenyl]cyclohexane) (30 nm)/Ir(tfmppy)2tpip (bis(4-trifluoromethylphenylpyridine-N,C2′)iridium(tetraphenylimido-diphosphinate)) (8 wt%): mCP [1,3-bis(N-carbazolyl)benzene] (10 nm)/QDPO or B-QDPO or BP-QDPO (30 nm)/LiF (1 nm)/Al (100 nm). These devices exhibited decent performances with a peak current efficiency above 80 cd A−1 and an external quantum efficiency above 20% as well as negligible efficiency roll-off.

A convenient metal-free sequential decarbonylative annulation of unactivated alkenes for the construction of quinazolinones and dihydroisoquinolinones has been developed. This strategy features the oxidative decarbonylation of various secondary and tertiary alkyl aldehydes with N-cyanamide alkenes for the cascade construction of C–C/C–N bonds.

A solvent controlled regioselective metal-free synthesis of iodo-substituted N-heterocycles has been developed. This protocol undergoes a cascade iodination/cyclization/oxidation/aromatization pathway to afford multi-halogenated quinolines from readily available propargylamines under mild conditions.

A solvent controlled regioselective metal-free synthesis of iodo-substituted N-heterocycles has been developed. This protocol undergoes a cascade iodination/cyclization/oxidation/aromatization pathway to afford multi-halogenated quinolines from readily available propargylamines under mild conditions.

A novel metal-free tandem oxidative coupling process for the synthesis of hemiaminal ethers has been developed. This protocol could be applied for the C–N bond formation of electron-deficient trizoles, tetrazoles, carbazoles and indazoles with primary alcohols.

A convenient oxidative sulfenylation method for the formation of various sulfenyl amides has been reported. Arenesulfonyl hydrazine as a sulfur source in the presence of a manganese salt can activate the sp3 C–H bond of N-methyl amides through a free-radical pathway using di-tert-butyl peroxide (DTBP).

A versatile metal-free synthesis of allylic N-heterocycles has been developed using a TBAI/TBHP oxidation system. This general protocol could be applied for the C–N bond formation of electron-deficient phthalimides, imidazoles, triazoles, and sulfonamides with cyclic and acylic olefins. The practical use of the method is demonstrated by the amidation of functionalized biologically active substrates.

A ytterbium(III)-indapybox catalysed enantioselective decarboxylative addition reaction of β-ketoacids to isatins is described. The biologically important 3-hydroxy oxindoles were obtained in high yields and excellent enantioselectivities.

On account of the broad utilities of organophosphorus compounds, the development of highly efficient and concise phosphination methods is significantly important and urgent. Herein, we disclose a novel method for the synthesis of phosphorylated heterocycles: versatile intermediate propargylamines serving as a new type of radical acceptors incorporated in P-radicals via a photocatalytic strategy. This reaction proceeds through a cascade phosphinoylation/cyclization/oxidation/aromatization pathway using readily available starting materials under mild conditions of light with excellent atom economy, catalyzed by AgOAc or fac-Ir(ppy)3. One of the phosphorylated quinolines was selected, as an example, as an electron-transporting material for fabricating phosphorescence organic light-emitting diodes displaying excellent electroluminescence performances with a maximum external quantum efficiency of 21.9% with negligible efficiency roll-off ratios.

A convenient oxidative sulfenylation method for the formation of various sulfenyl amides has been reported. Arenesulfonyl hydrazine as a sulfur source in the presence of a manganese salt can activate the sp3 C–H bond of N-methyl amides through a free-radical pathway using di-tert-butyl peroxide (DTBP).

A ytterbium(III)-indapybox catalysed enantioselective decarboxylative addition reaction of β-ketoacids to isatins is described. The biologically important 3-hydroxy oxindoles were obtained in high yields and excellent enantioselectivities.