A general and practical rhodium-catalyzed aminocarbonylation reaction of DMC with nitro compounds has been developed. DMC acted both as a C1 building block and a reaction medium, to give a wide range of acetamide compounds in very good yields.

A new procedure for the synthesis of aryl methyl sulfides from dimethyl carbonate (DMC) and arylsulfonyl chlorides has been achieved. In this strategy, DMC plays a dual role as both, C1 building block and green solvent. Arylsulfonyl chlorides served as the sulfur precursors, and a variety of aryl methyl sulfides were obtained in moderate to excellent yields with good functional group tolerance. Additionally, alkylsulfonyl chloride and dibenzyl carbonate are proven to be suitable substrates as well.

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 N-(o-iodoaryl)­acrylamides and o-alkynylphenols/o-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.