Unless otherwise noted, materials were obtained from commercial suppliers and used without further purification. NMR spectra were recorded on a Bruker AV-400 ( 1 H: 400 MHz, 13 C:100 Hz) spectrometer using TMS as internal reference. Chemical shifts (δ) and coupling constants (J) were expressed in ppm and Hz, respectively. The following calibration was used: CDCl3 δ = 7.26 and 77.16 ppm. High resolution mass spectra (HRMS) were measured using electrospray ionization (ESI) and the time-of-flight (TOF) mass analyzer. The instrument for electrolysis is DC regulated power supply (HY3005M, made in China). The anode electrode and cathode electrode all are Pt (1.5 × 1.5 × 0.3 cm 3 ). These electrodes are commercially available from GaossUnion, China.Commercially available compounds were used as received without further purification.The start materials including substituted 4-methyl-N-(2-vinylphenyl)benzenesulfonamide compounds, 1 Nsubstituted 2-vinylanilines, all were known and synthesized according to literature procedures. 2 Experimental ProcedureGeneral procedure A for the electrosynthesis of diamination indoline: An undivided cell was equipped with a magnet stirrer, platinum plate (1.5 × 1.5 × 0.3 cm 3 ) electrode, as the working electrode and counter electrode. The substrate 2-vinyl aniline 1 (0.3 mmol), amine 2 (0.3 mmol), Me4NI (20 mol %, 12.1 mg) and NH4PF6 (0.3 mmol, 49.9 mg) were added to the solvent CH3CN/H2O (5 mL/1 mL). The electrolysis was conducted in an undivided cell at a constant current of 5 mA at room temperature (25°C). After the reaction was completed, the solvent was removed under reduced pressure and the remaining crude product was purified by column chromatography over silica gel (PE/EtOAc = 20/1) to afford the corresponding indoline product.General procedure B for the electrosynthesis of indole: An undivided cell was equipped with a magnet stirrer, platinum plate (1.5 × 1.5 × 0.3 cm 3 ) electrode, as the working electrode and counter electrode. The substrate 2vinyl aniline 1 (0.3 mmol), Me4NI (0.3 mmol, 60.3 mg) and KSCN (0.3 mmol, 29 mg) were added to the solvent CH3CN/H2O (5 mL/1 mL). The electrolysis was conducted in an undivided cell at a constant current of 5 mA at oil bath (80°C). After the reaction was completed, the solvent was removed under reduced pressure and the remaining crude product was purified by column chromatography over silica gel (PE/EA = 30/1) to afford the corresponding indole product.Gram-scale synthesis of 3aa: An undivided cell was equipped with a magnet stirrer, platinum plate (1.5 × 1.5 × 0.3 cm 3 ) electrode, as the working electrode and counter electrode. The substrate 2-vinyl aniline 1a (6 mmol, 1.64 g), phenylamine 2a (6 mmol, 559 μL), Me4NI (3 mmol, 603.2 mg) and Me4NPF6 (6 mmol, 978 mg) were added to the solvent CH3CN/H2O (100 mL/20 mL). The electrolysis was electrolyzed (I = 20 mA, 8.9 mA/cm 2 ) in an undivided cell at room temperature (25°C). After the reaction was completed (about 24 h), the reaction system was allowed to attain room temperature. Then the rea...

A regioselectivity switchable aerobic Wacker-Tsuji oxidation has been developed using catalytic tert-butyl nitrite as a simple organic redox cocatalyst. By solely switching the solvent, either substituted aldehydes or ketones could be prepared under mild aerobic conditions in good yields, respectively. A mechanistic explanation for the selectivity control is proposed.

An efficient NH 4 I-mediated intermolecular annulation of methyl N-heteroaromatics with amines/amino acids was developed by virtue of anodic oxidation, providing a variety of functionalized imidazo-fused N-heterocycles with good to excellent yields. The practicality of this protocol was demonstrated by the readily available starting materials, broad substrate scope, water tolerance, scalability, and the diverse transformations of the electrolysis product.

An electrochemical three-component cyclization was developed under metal-free conditions, which provides a novel and facile approach for the construction of cyanide-functionalization imidazo-fused N-heterocycles. A variety of cyanide-functionalization imidazo-fused N-heterocycles can be obtained from easily available methyl Nheteroaromatics, primary alkylamines, and trimethylsilyl cyanide with good to excellent yields. The reaction features a broad scope of substrates, scalability, and mild conditions.

In this work, an organopromoted metal-free pharmaceutical-oriented selectivity-switchable benzylic oxidation was developed, affording mono-, di-, and trioxygenation products, respectively, using oxygen as the oxidant under mild conditions. This process facilitates dioxygenation of 2,6-benzylic positions of heterocycles, which could be inhibited by heterocycle chelation to the metal cocatalysts. Enantiopure chiral ketones could also be prepared. The noninvolvement of transition metals and toxins avoids metal or hazardous residues, consequently ensuring a final-stage gram-scale synthesis of Lenperone.