Palladium-catalyzed double carbonylation of propargyl amines and aryl halides to access 1-aroyl-3-aryl-1,5-dihydro-2H-pyrrol-2-ones

Abstract

A palladium-catalyzed carbonylative procedure for the synthesis of 1-aroyl-3-aryl-1,5-dihydro-2H-pyrrol-2-ones from propargyl amines and aryl halides with TFBen as the CO source has been developed.

TFBen (Benzene‐1,3,5‐triyl triformate): A Powerful and Versatile CO Surrogate

“…Inspired by the positive result of the above TFBen-involved cyclocarbonylation reaction of propargyl amines, Wu and coworkers added aryl halides into the palladium-catalyzed carbonylative reaction system and not surprisingly, diverse aryl-substituted 2-oxo-2,5-dihydropyrroles were obtained in good yields (Scheme 11a). [25] Compared with the previously reported work by the same authors, [24] this double carbonylative reaction underwent a different pathway, which involved a linear carbonylated amide as the key intermediate other than a cyclized lactam intermediate. Except for aryl iodides, aryl bromides and vinyl bromides also acted as viable substrates in the transformation.…”

“…[26] By using CH 3 CN as the solvent, the palladium-catalyzed double carbonylative reaction of propargyl amines and benzyl chlorides occurred smoothly to deliver the structurally diverse 1,5-dihydro-2Hpyrrol-2-one products in good to excellent yields. The proposed reaction mechanism is similar to that of the carbonylative reaction containing aryl halides, [25] which involves a mono-carbonylated product from coupling of propargyl amine and benzyl chloride as the key intermediate.…”

Progress in the Synthesis of Aroyl Compounds

“…13). 2020 年, 吴小峰课题组 [37] 又报道了以炔丙基胺和 卤代芳烃为原料合成 N-芳甲酰基类吡咯酮的新方法. 该反应以乙酰丙酮钯为催化剂, 1,1'-双(二苯基膦)二茂 铁(DPPF)为配体, 苯-1,3,5-三甲酸三酯(TFBen)为羰基 源, 收率达 91%.…”

Iodine-Promoted Formal [3+2] Cycloaddition of Enaminone: Access to 2-Hydroxy-1,2-dihydro-pyrrol-3-ones with Quaternary Carbon Center

“…However, compared with the synthesis of 1 H -pyrrol-2-ones, there are only a few established methods for the construction of 1 H -pyrrol-3­(2 H )-ones that have been reported . As the carbonyl group of pyrrol-3­(2 H )-ones is prone to keto-enol equilibrium with 3-hydroxyl pyrrole, it is difficult for 1 H -pyrrol-3­(2 H )-ones to exist stably .…”