Heck and oxidative boron Heck reactions employing Pd(II) supported amphiphilized polyethyleneimine‐functionalized MCM‐41 (MCM‐41@aPEI‐Pd) as an efficient and recyclable nanocatalyst

Abstract

A novel nanocatalyst was developed based on covalent surface functionalization of MCM‐41 with polyethyleneimine (PEI) using [3‐(2,3‐Epoxypropoxy)propyl] trimethoxysilane (EPO) as a cross‐linker. Amine functional groups on the surface of MCM‐41 were then conjugated with iodododecane to render an amphiphilic property to the catalyst. Palladium (II) was finally immobilized onto the MCM‐41@PEI‐dodecane and the resulted MCM‐41@aPEI‐Pd nanocatalyst was characterized by FT‐IR, TEM, ICP‐AES and XPS. Our designed nanocatalyst with a distinguished core‐shell structure and Pd2+ ions as catalytic centers was explored as an efficient and recyclable catalyst for Heck and oxidative boron Heck coupling reactions. In Heck coupling reaction, the catalytic activity of MCM‐41@aPEI‐Pd in the presence of triethylamine as base led to very high yields and selectivity. Meanwhile, the MCM‐41@aPEI‐Pd as the first semi‐heterogeneous palladium catalyst was examined in the C‐4 regioselective arylation of coumarin via the direct C‐H activation and the moderate to excellent yields were obtained toward different functional groups. Leaching test indicated the high stability of palladium on the surface of MCM‐41@aPEI‐Pd as it could be recycled for several runs without significant loss of its catalytic activity.

Synthesis and Characterization of Palladium Supported Amino Functionalized Magnetic-MOF-MIL-101 as an Efficient and Recoverable Catalyst for Mizoroki–Heck Cross-Coupling

“…A variety of reagents such as bromo and chloro derivatives with unactivated alkenes were utilized for synthesizing Heck products, the most industrially relevant studies were conducted with aryl bromides [7]. In most cases, the coupling reactions occur in the presence of palladium as a catalyst [8]. Other metals are also used to catalyze the Heck reaction, for example, nickel having many advantages being abundant, non-toxic, and cost effective [9].…”

Functionalized Silicas for Metal‐Free and Metal‐Based Catalytic Applications: A Review in Perspective of Green Chemistry

“…On the other hand, there are few composites which have the constitutes that chemically interact with each other. Graphene oxide, polyethylene glycol, polyethyleneimine, allyl calixarene, and polymerized cobalt(III) complex are involved in the chemical interaction with FSs during the formation of FS composites . The non‐FSs have formed the composites with the polymers containing significant functional groups.…”

“…In spite of displaying very good catalytic activity, these palladium(0)‐FS catalysts demonstrate excellent reusability because the leaching of palladium(0) active sites is greatly inhibited which befalls through the strong chemical interaction between palladium(0) and FSs. Like palladium(0) FS catalysts, palladium(II) ions immobilized on FSs are also effectual as the catalysts for Suzuki‐Miyaura coupling, Heck‐Mizoroki coupling and Hiyama coupling . Interestingly, N. Vucetic et al have dispersed palladium(II) on IL FS which exhibits the best catalytic activity (turnover frequency (TOF)=22000 h −1 ) than all other catalysts reported in the literature for Heck‐Mizoroki coupling befalling between iodobenzene and methacrylate in presence of a base.…”

V‐N‐C catalysts anchored to mesoporous Al‐SBA‐15 with tailorable pore sizes for the synthesis of spirooxindole dihydroquinazolinones derivatives

“…These materials serve as an exceptional choice for such applications. Moreover, they offer high specific surface areas, large and defined pore sizes, defined surface acidity, and excellent mechanical and thermal stability . In this regard, the substituents such as aluminum, titanium and zirconium can be incorporated into the silica framework to obtain materials for applications such as catalysis and ion exchange.…”