Palladium-Catalyzed Carbonylative Synthesis of α,β-Unsaturated Amides from Styrenes and Nitroarenes

Abstract

A procedure on palladium-catalyzed selective aminocarbonylation of styrenes with nitroarenes for the synthesis of α,β-unsaturated amides has been developed. A range of substituted α,β-unsaturated amides were synthesized in moderate to good yields. Interestingly, nitroarenes act as both a nitrogen source and oxidant, and Mo(CO) acts as a solid CO source and reductant in this catalytic system.

Direct Access to Amides from Nitro‐Compounds via Aminocarbonylation and Amidation Reactions: A Minireview

“…In 1980, Yamazaki et al disclosed that the reaction between nitroarenes 1, carbon monoxide and benzene in the presence of Rh 4 (CO) 12 or Rh 6 (CO) 16 gave N-aryl benzamides 32 via the reductive carbonylation of nitroarenes and subsequent addition of benzene to the resulting aryl isocyanates (Scheme 9). [19] But the yields of the products were moderate only since aniline was isolated as the side product.…”

Progress in the Synthesis of Aroyl Compounds

“…2018 年, 吴小锋课题组 [35] 以 Mo(CO) 6 为羰基源, 芳 基乙烯和硝基取代的芳烃为原料, 在乙酰丙酮钯催化条 件下合成了芳乙烯基取代的酰胺类化合物, 收率达 86%, 该反应底物廉价易得. 在该反应中 Mo(CO) 6 起到 了还原剂和羰基源的双重作用, 机理研究表明, 硝基芳 烃在钯催化剂的循环中起到重要作用(Eq.…”

Recent Advances in the Functionalization of Hydrocarbons: Synthesis of Amides and its Derivatives

“…Peng et al. explored a palladium‐catalyzed aminocarbonylation method for the synthesis of α,β‐unsaturated amides from alkenes and nitroarenes (Scheme a) . The optimal conditions for this transformation were found to be Pd(acac) 2 as a catalyst, DPPP as a ligand, benzenesulfonic acid monohydrate as an additive, and Mo(CO) 6 as the solid CO source.…”