2-Alkynylanilines are attractive starting materials in indole synthesis because of their ready availability. Herein, a one-pot stepwise procedure is reported for efficient construction of multisubstituted oxocino[4,3,2-cd]indoles from 2-alkynylanilines and 2-alkynylbenzaldoximes. The method comprises the oxidative dearomatization of 2-alkynylanilines, the silver-catalyzed [3+3] cycloaddition with 2-alkynylbenzaldoximes, and subsequent thermal radical skeletal rearrangement and aromatization.

The formation of carbon–carbon bonds through the functionalization of aromatic carbon–nitrogen bonds is a highly attractive synthetic strategy in the synthesis of aromatic molecules. In this paper, we report a novel aromatic carbon–nitrogen bond functionalization reaction by using a simple dearomatization strategy. Through this process para-substituted anilines serve as a potential aryl source in the construction of a range of functionalized aromatic molecules, such as quaternary carbon centers, α-keto esters, and aldehydes.

2-Alkynylanilines are attractive starting materials in indole synthesis because of their ready availability. Herein, a one-pot stepwise procedure is reported for efficient construction of multisubstituted oxocino[4,3,2-cd]indoles from 2-alkynylanilines and 2-alkynylbenzaldoximes. The method comprises the oxidative dearomatization of 2-alkynylanilines, the silver-catalyzed [3+3] cycloaddition with 2-alkynylbenzaldoximes, and subsequent thermal radical skeletal rearrangement and aromatization.

The formation of carbon–carbon bonds through the functionalization of aromatic carbon–nitrogen bonds is a highly attractive synthetic strategy in the synthesis of aromatic molecules. In this paper, we report a novel aromatic carbon–nitrogen bond functionalization reaction by using a simple dearomatization strategy. Through this process para-substituted anilines serve as a potential aryl source in the construction of a range of functionalized aromatic molecules, such as quaternary carbon centers, α-keto esters, and aldehydes.

A method to directly convert 2-alkynylphenols to 3,4-difunctionalized benzofurans and polycyclic benzofurans was developed. This protocol involves a hypervalent-iodine-mediated oxidative dearomatization to break the aromaticity of 2-alkynylphenols, and a palladium-catalyzed domino reaction to install two functional groups at the C3 and the C4 positions and restore the aromaticity of benzofurans.

An efficient method to construct oxa-aza spirobicycles via an iodine(III)-mediated tandem carbon-hydrogen bond oxidation with the combination of iodobenzene diacetate and tetrabutylammonium iodide is reported.

A selective C3C3 oxidative cross-coupling between unactivated anilines and indoles catalyzed by copper bromide together with iodobenzene diacetate as the oxidant is described. This methodology provides a novel approach to biaryl synthesis.

Aziridination of N-tosylimines with activated methylene compounds induced by iodobenzene diacetate [PhI(OAc)₂] and tetrabutylammonium bromide [Bu₄NBr] afforded the corresponding 2,2-difunctionalized aziridines in good yields with the aid of a catalytic amount of base. The reaction is hypothesized to proceed via a tandem nucleophilic addition-oxidative cyclization pathway.

An efficient one-pot oxidative heteroannulation of N-sulfonylaniline derivatives with styrene derivatives for the rapid construction of 5-aminocoumaran derivatives is reported. Copper trifluoromethanesulfonate was found to be an excellent catalyst for the oxidative heteroannulation reactions with low reactive styrenes.

An efficient oxidative cyclopropanation of the Michael adducts of nitroolefins with activated methylene compounds by the combination of iodobenzene diacetate and tetrabutylammonium iodide is reported. Highly functionalized nitrocyclopropanes are synthesized in moderate to good yields via the Michael addition and cyclopropanation with high diastereoselectivity and enantioselectivity under mild conditions.