Trifluoromethylthiolation Carbonylation of Unactivated Alkenes via Distal Migration.

Sulfur-containing compounds represent a significant category of organic compounds, and the introduction of sulfur groups into organic compounds can effectively enhance their biological activity and synthetic diversity. Although a variety of difunctionalization reactions of alkenes based on sulfur radicals have been documented, significant challenges remain in the carbonylative difunctionalization of unactivated alkenes by the addition of a sulfur radical. Herein, we present a trifluoromethylthiolative carbonylation reaction of unactivated alkenes, which goes through the addition of a trifluoromethylthiol radical to unactivated alkenes and then carbonylation of the newly generated carbon radical intermediate.

Palladium-Catalyzed Domino Carbopalladation/Carbonylative Cyclization: Synthesis of Heterocycles bearing Oxindoles and 3-Acylbenzofuran/3-Acylindole Moieties.

A novel and straightforward methodology for palladium-catalyzed carbopalladation-initiated domino carbonylative cyclization to construct bisheterocycles has been established. With TFBen as an efficient and convenient CO source, the protocol is capable of generating oxindole and 3-acylbenzofuran/3-acylindole moieties from the corresponding -(-iodoaryl)acrylamides and -alkynylphenols/-alkynylanilines with the formation of three C-C bonds and one C-O/C-N bond in a single one-step operation. A wide range of bisheterocycles bearing oxindoles and 3-acylbenzofurans/3-acylindoles were prepared in moderate to excellent yields with good functional group tolerance.

A novel construction of acetamides from rhodium-catalyzed aminocarbonylation of DMC with nitro compounds.

Dimethyl carbonate (DMC), an environment-friendly compound prepared from CO2, shows diverse reactivities. In this communication, an efficient procedure using DMC as both a C1 building block and solvent in the aminocarbonylation reaction with nitro compounds has been developed. W(CO)6 acts both a CO source and a reductant here.