Palladium Nanoparticles Supported on ZIF-8 As an Efficient Heterogeneous Catalyst for Aminocarbonylation

Abstract

Pd nanoparticles supported on ZIF-8 (PdNPs/ZIF-8) are described as an efficient heterogeneous catalyst for the aminocarbonylation of bromoarenes in the presence of phosphines and iodoarenes under phosphine-free conditions. The catalyst can be readily prepared and is air-stable. The palladium loading can be as low as 1 wt %, and the catalyst was recycled four times with negligible change in catalytic performance. A variety of pharmaceutically important amides was readily synthesized. A TON of 2540 was easily achieved in a batch reaction by scaling up to a gram scale. The catalyst reported can also be applied to the synthesis of cyclic and primary amides as well as an alkoxycarbonylation reaction to form an ester.

Amine-functionalized MIL-53(Al) with embedded ruthenium nanoparticles as a highly efficient catalyst for the hydrolytic dehydrogenation of ammonia borane

“…7 Due to their high specic surface areas, variety of structures, and chemical stability, MOFs have drawn increasing attention for applications in drug delivery, gas adsorption, and catalytic reactions. [8][9][10] The facile functionalization of the internal pore surface is another important characteristic of MOFs. 11 To date, a series of functionalized MOFs that incorporate a variety of functional groups (e.g., -OH and -NH 2 ) has been successfully prepared.…”

Ligand-free Pd(0)/SiO2-catalyzed aminocarbonylation of aryl iodides to amides under atmospheric CO pressure

“…In the absence of catalyst, no product was obtained. In the case of only using Pd/ SiO 2 without K 2 CO 3 , a small amount of the desired product (10%) was obtained ( supports provided the desired product in moderate to good yields (from 42% to 84%) under similar reaction conditions (entries [11][12][13][14][15][16][17][18]. Therefore, Pd/SiO 2 catalyst was found to be the optimum catalyst for the carbonylation of iodobenzene.…”

“…It is noteworthy that p-substituted amines gave a slightly decreased yield compared with that of o-and m-substituted amines. The substituted amines with electron-withdrawing halogen groups were also tolerated, and gave 66% to 91% yields to the corresponding amides in the order I > Br > Cl (entries [18][19][20][21]. When the amines that have a substituent attached to the amino group were used, the desired products were obtained in moderate yields (entries 22).…”

Concise Synthesis of Vesnarinone and Its Analogues by Using Pd‐Catalyzed C–N Bond‐Forming Reactions

“…In light of our recent work on sustainable amide syntheses based on supported palladium nanoparticles catalyzed aminocarbonylations of aryl halides, [6] we envisioned that a wig amination and a supported Pd nanoparticles catalyzed aminocarbonylation were utilized as the two key reactions to prepare vesnarinone in an overall yield of 73 %. Sixteen analogues were also synthesized in up to 89 % overall yield.…”