Divergent synthesis of carbamates and N-methyl carbamates from dimethyl carbonate and nitroarenes with Mo(CO)6 as a multiple promoter.

Dialkyl carbonates are green and versatile reagents that can be used in alkylation and alkoxycarbonylation reactions. Herein, we disclosed a reductive methoxycarbonylation of aromatic nitro compounds with dimethyl carbonate for the construction of diverse carbamates and N-methyl carbamates. Using Mo(CO)6 as a multiple promoter, different nitroarenes were smoothly transformed into the corresponding carbamates in yields between 27 and 94% using DMC as both solvent and reagent. It is worth noting that the choice of different bases allowed the desired products to be controlled: K3PO4 favoured the formation of carbamates as the primary product, whereas DBU facilitated the formation of N-methyl carbamates as the main product.

Direct synthesis of phthalimides via palladium-catalysed double carbonylation of o-dihaloarenes with nitroarenes.

The direct carbonylation of readily available nitro compounds is more attractive and straightforward than the use of traditional amines as nucleophiles. Herein, a practical palladium-catalysed double carbonylation of nitroarenes with o-dihaloarenes has been developed for the construction of various N-aryl phthalimides. Key to the success of this transformation is the use of Mo(CO)6, which acts as both a reducing agent and a solid carbonyl source. A wide range of nitroarenes and o-dihaloarenes as well as o-iodobenzoic acids reacted smoothly to give phthalimides in 27-94% yields.

Palladium-Catalyzed Reductive Double Carbonylation of Nitroarenes with Aryl Halides Using Mo(CO)6 as a Reductant and Carbonyl Source.

A new palladium-catalyzed reductive double carbonylation of nitroarenes with aryl halides for the synthesis of benzoxazin-4-ones has been reported. The key to success was the use of Mo(CO)6 as a reductant and bench-stable solid carbonyl sources. Various aryl iodides, bromides, and trifluoromethanesulfonates are suitable reaction partners and produce corresponding benzoxazin-4-one derivatives in moderate to good yields. Preliminary mechanistic studies indicate that nitrosoarene was first generated as the key intermediate through nitro reduction. Remarkably, this method avoids the use of toxic CO gas and is further applied to the late-stage modification of estrone.