Palladium‐Catalyzed Carbonylative Synthesis of 1,5‐Dihydro‐2H‐pyrrol‐2‐ones from Propargyl Amines and Benzyl Chlorides

Abstract

A palladium-catalyzed double carbonylation of propargyl amines and benzyl chlorides employing benzene-1,3,5-triyl triformate (TFBen) as the CO source has been developed. By using this protocol, various 1,5-dihydro-2H-pyrrol-2-ones were produced in good yields.

Recent Advances in the Synthesis of Five‐membered Nitrogen Heterocycles Induced by Palladium Ions and Complexes

“…[49] The group of Wu has exploited carbonylation of propargylamines using TFBen as CO surrogate in a number of studies. [50] In a recent publication [51] they executed a double carbonylation process using Pd(OAc) 2 and applying the so-called "in-ex tube" technique. [52] In detail, propargylamines, the catalyst, and ligand dppf (L7) were added into the ex-tube, whereas the in-tube contained TFBen.…”

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

“…Noteworthy is that benzyl chlorides could also be applied as starting material for the carbonylative synthesis of 1,5dihydro-2H-pyrrol-2-ones (Scheme 11b). [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.…”

Regioselective Construction of Indolylated Cyclic Tetrasubstituted Carbon Centers through Brønsted Acid‐Catalyzed Dearomative Skeletal Rearrangement of Azofurans

“…[4g] With these appealing contributions in mind, many reliable synthetic strategies have been established to access 1,5-dihydro-2H-pyrrol-2ones over the years. [5] However, there are few reports on the assembly of N-substituted 2H-pyrrol-2-ones bearing cyclic tetrasubstituted carbons, [6] probably because of the inherent difficulty in overcoming the congested nature of tetrasubstituted carbons. [7] Consequently, developing a new and widely used synthetic technology for the synthesis of cyclic tetrasubstituted carbon-containing pyrrol-2-ones is highly desirable, considering the potential of using these molecules for downstream studies in medicinal chemistry.…”