Bifunctional Heterogeneous Ru/POP Catalyst Embedded with Alkali for the N-Formylation of Amine and CO₂

Abstract

CO 2 as a C1 building block for the N-formylation reaction is attracting much attention. In general, the N-formylation reaction requires the participation of alkali, which can break the equilibrium to promote the reaction process. We developed a After Ru metalationheterogeneous catalyst with an alkaline functional group based on a porous organic polymer (denoted as Ru-PPh 3 -SO 3 Na@POPs) by the copolymerization of vinyl-functionalized PPh 3 (3v-PPh 3 ) and sodium-4vinylbenzenesulfonate. After Ru metalation, the catalyst obtained a high TON without the addition of alkali under mild conditions. The Ru-PPh 3 -SO 3 Na@POP catalyst can immobilize metals and alkali efficiently on porous organic polymers, showing excellent performance and good stability for the N-formylation reaction of amine and CO 2 .

Highly Efficient Heterogeneous Pd@POPs Catalyst for the N-Formylation of Amine and CO2

“…As we know that the N-formylation reaction mechanism ( Figure 5) is similar in most literatures, CO2 is reduced to formic acid in a hydrogen atmosphere, and then reacts with amine to form amides [17,29,31]. We also demonstrated the reaction mechanism in a previous work [32]. As we know that the N-formylation reaction mechanism ( Figure 5) is similar in most literatures, CO 2 is reduced to formic acid in a hydrogen atmosphere, and then reacts with amine to form amides [17,29,31].…”

“…As we know that the N-formylation reaction mechanism ( Figure 5) is similar in most literatures, CO2 is reduced to formic acid in a hydrogen atmosphere, and then reacts with amine to form amides [17,29,31]. We also demonstrated the reaction mechanism in a previous work [32].…”

Bifunctional Ru‐loaded Porous Organic Polymers with Pyridine Functionality: Recyclable Catalysts for N‐Formylation of Amines with CO2 and H2

“…The SEM (scanning electron microscopy) and TEM (transmission electron microscopy) images in Figures 2a and 2b display rough morphologies with abundant pores on the surface and in the internal structure, which further demonstrate the porosity of Ru/POP 3 ‐Py&PPh 3 . In addition, Ru/POP 3 ‐Py&PPh 3 had a good CO 2 uptake capacity (up to 41.5 mg g −1 under 1 bar at 298 k), and the result was similar to those of the phosphine‐rich polymers‐supported catalysts in the literature [22,23] . The CO 2 uptake capacity of Ru/POP‐PPh 3 was also detected and exhibited a slightly higher capacity (45.2 mg g −1 ) than Ru/POP 3 ‐Py&PPh 3 , which may be owing to the relatively high surface area of the catalyst.…”

“…Mesoporous imine‐functionalized POP‐supported Pd catalyst (Imine‐POP@Pd) [20] and pyridine‐functionalized POP‐immobilized Ru (CarPy‐CMP@Ru) [21] were developed for the N‐formylation of amines with CO 2 /H 2 by Liu's group. More recently, Ding and Yan reported a Ru−PPh 3 −SO 3 Na@POP catalyst that incorporated SO 3 Na as the base for the N‐formylation of amines, which was mainly effective for the N‐formylation of secondary aliphatic amines [22] . Alkali is generally required as a co‐catalyst in the N‐formylation of amines with CO 2 /H 2 , and it is difficult to be recovered in a homogeneous reaction.…”

Homogeneous (De)hydrogenative Catalysis for Circular Chemistry – Using Waste as a Resource

“…Several examples of heterogeneous catalysts mostly based on precious metals have also been reported in recent years for the N‐formylation of amines using CO 2 /H 2 [96–98] . However, pincer catalysts, for example, the one reported by Ding (TON of 1.94 million for the N‐formylation of morpholine in 97 h at 120 °C and PCO 2 =PH 2 =35 bar and that by Bernskoetter (TON=4260 in 4 h at 120 °C and PCO 2 =PH 2 =34.5 bar) still remain to be more active catalysts in this direction.…”