Cascade Electrochemical Aerobic Oxygenation of 2-Substituted Indoles and Electrochemical [5 + 3] Annulation with Amidines: Access to Eight-Membered Benzo[1,3,5]triazocin-6(5H)-ones.

The cascade electrochemical C3-selective aerobic oxygenation of 2-substituted indoles and electrochemical [5 + 3] annulation with amidines through an undivided cell galvanostatic method employing molecular oxygen and "electricity" as green oxidants was developed. This protocol provides an efficient and direct approach to eight-membered benzo[1,3,5]triazocin-6(5H)-ones. Mechanistic studies suggested that two subsequent electrochemical processes both proceeded through radical pathways.

Rhodaelectro-Catalyzed Decarboxylative Cross-Dehydrogenative Coupling of Indole-3-carboxylic Acids and Olefins via Weakly Coordinating Carboxyl Groups.

A rhodaelectro-catalyzed C2-H selectively decarboxylative alkenylation of 3-carboxy-1H-indoles employing electricity as the traceless terminal oxidant has been accomplished. The weakly coordinating carboxyl group serves as the traceless directing groups. External oxidant-free in an undivided cell with constant current in aqueous solution ensures the decarboxylative C-H alkenylation to be viable and sustainable.

Chemodivergent Synthesis of Indeno[1,2-b]indoles and Isoindolo[2,1-a]indoles via Mn(III)-Mediated or Electrochemical Intramolecular Radical Cross-Dehydrogenative Coupling.

Chemodivergent synthesis of indeno[1,2-b]indoles and isoindolo[2,1-a]indoles from the same starting materials involving radical cross-dehydrogenative couplings have been developed. Mn(OAc)3·2H2O selectively promoted an intramolecular radical C-H/C-H dehydrogenative coupling reaction to provide indeno[1,2-b]indoles, while an intramolecular radical C-H/N-H dehydrogenative coupling reaction could proceed via electrochemistry to deliver isoindolo[2,1-a]indoles. Plausible mechanisms of the chemodivergent reactions were proposed.

Scalable Electrochemical Aerobic Oxygenation of Indoles to Isatins without Electron Transfer Mediators by Merging with an Oxygen Reduction Reaction.

An approach to electrochemical oxygenation of indoles leading to isatins was developed by merging with a complementary cathode oxygen reduction reaction. The features of this green protocol include the use of molecular oxygen as the sole oxidant, it being free of an electron transfer mediator, and gram-scale preparation. Mechanistic studies suggested a radical process, and the two oxygen atoms in the isatins were both most likely from molecular oxygen. A detailed mechanism of the reaction utilizing density functional theory calculations was elucidated.

Synthesis of Indole-Fused Six-, Seven-, or Eight-Membered N,O-Heterocycles via Rhodium-Catalyzed NH-Indole-Directed C-H Acetoxylation/Hydrolysis/Annulation.

We report herein the facile synthesis of indole-fused six-, seven-, or eight-membered N,O-heterocycles through rhodium-catalyzed C-H acetoxylation/hydrolysis/annulation. The notable features of this method include C-H acetoxylation using NH-indole as the intrinsic directing group, high functional group compatibility, and construction of indole-fused medium-sized rings.

Rhodium-Catalyzed Oxidative Annulation of 2- or 7-Arylindoles with Alkenes/Alkynes Using Molecular Oxygen as the Sole Oxidant Enabled by Quaternary Ammonium Salt.

Developing an efficient catalytic system using molecular oxygen as the oxidant for rhodium-catalyzed cross-dehydrogenative coupling remains highly desirable. Herein, rhodium-catalyzed oxidative annulation of 2- or 7-phenyl-1H-indoles with alkenes or alkynes to assemble valuable 6H-isoindolo[2,1-a]indoles, pyrrolo[3,2,1-de]phenanthridines, or indolo[2,1-a]isoquinolines using the atmospheric pressure of air as the sole oxidant enabled by quaternary ammonium salt has been accomplished. Mechanistic studies provided evidence for the fast intramolecular aza-Michael reaction and aerobic reoxidation of Rh(I)/Rh(III), facilitated by the addition of quaternary ammonium salt.

Intermolecular Dearomatization of Naphthalene Derivatives by Photoredox-Catalyzed 1,2-Hydroalkylation.

An intermolecular hydroalkylative dearomatization of naphthalenes with commercially available α-amino acids is achieved via visible-light photoredox catalysis. With an organic photocatalyst, a series of multi-substituted 1,2-dihydronaphthalenes are obtained in good-to-excellent yields. Intriguingly, by tuning the substituents at the C2 position of naphthalenes, formal dearomative [3+2] cycloadditions occur exclusively via a hydroalkylative dearomatization-cyclization sequence. This overall redox-neutral method features mild reaction conditions, good tolerance of functionalities, and operational simplicity. Diverse downstream elaborations of the products are demonstrated. Preliminary mechanistic studies suggest the involvement of a radical-radical coupling pathway.