The Current Status of Heterogeneous Palladium Catalysed Heck and Suzuki Cross-Coupling Reactions

Abstract

In the last 30 years, C–C cross coupling reactions have become a reliable technique in organic synthesis due their versatility and efficiency. While drawbacks have been experienced on an industrial scale with the use of homogenous systems, many attempts have been made to facilitate a heterogeneous renaissance. Thus, this review gives an overview of the current status of the use of heterogeneous catalysts particularly in Suzuki and Heck reactions. Most recent developments focus on palladium immobilised or supported on various classes of supports, thus this review highlights and discuss contributions of the last decade.

Direct Mechanocatalysis: Palladium as Milling Media and Catalyst in the Mechanochemical Suzuki Polymerization

“…The formation of CÀCb onds is an important tool in organic [1,2] and polymer chemistry. [3][4][5] There are many crosscoupling reactions established to create those bonds such as Negishi, [6,7] Mizoroki-Heck, [8,9] Sonogashira, [10] and Suzuki-Miyaura [5,11] coupling.I na ll these,p alladium species are required as acatalyst, mainly brought in as complexes such as tetrakis(triphenylphosphine)palladium(0). [1] In most cases, the catalyzed reactions are run homogeneously,a lthough there are discussions and studies in the literature about heterogeneous analogues.…”

Supramolecular photocatalyst of Palladium (II) Encapsulated within Dendrimer on TiO2 nanoparticles for Photo‐induced Suzuki‐Miyaura and Sonogashira Cross‐Coupling reactions

“…These results proposed that the improved photoactivity predominantly benefits from the synergistic effects of Pd (II) amine‐terminated poly (triazine‐triamine) dendritic on TiO 2 nanoparticles that cause efficient separation and photogenerated electron–hole pairs and photoredox capability of nanocatalyst which all of these advantages due to the tuning of band gap of catalyst in the visible light region. It should be noted that there are many reports of cross‐coupling reactions catalyzed via homogeneous or heterogeneous processes, but most of them need to be conducted at elevated temperatures (≥100 °C), even under reflux conditions . This study shows that visible light irradiation can drive the same reactions on the Pd (II) [PTATAD] @ TiO 2 under much milder reaction conditions (27–30 °C), achieving good to excellent yields, and no additional additives such as co‐catalysts or phosphine ligands are required.…”

“…It should be noted that there are many reports of cross-coupling reactions catalyzed via homogeneous or heterogeneous processes, but most of them need to be conducted at elevated temperatures (≥100°C), even under reflux conditions. [53][54][55][56][57][58][59][60][61][62] This study shows that visible light irradiation can drive the same reactions on the Pd (II) [PTATAD] @ TiO 2 under much milder reaction conditions (27-30°C), achieving good to excellent yields, and no additional additives such as cocatalysts or phosphine ligands are required.…”

Integrating Reactors and Catalysts through Three‐Dimensional Printing: Efficiency and Reusability of an Impregnated Palladium on Silica Monolith in Sonogashira and Suzuki Reactions

“…Suzuki and Sonogashira reactions are paradigmatic transformations for the construction of carbon-carbon bonds and have been extensively used in organic synthesis for decades. [49,50] Initial studies of the catalytic activity of reactor/ monolith assembly (Figure 5a, b) focused on the following aspects: obtaining selectivity and high yields for the two transformations studied (Suzuki and copper-free Sonogashira); the inspection of palladium leaching on the monolith surface in the presence of reagents (boronic acids, alkynes, bases and solvents at high temperature); the reusability of the entire reactor/catalyst system and the possibility of applying this system to the synthesis of molecules by solution phase chemistry, at laboratory scale.…”