s, or keywords if they used Heck-type chemistry in their syntheses, because it became one of basic tools of organic preparations, a natural way to

http://aether.cmi.ua.ac.be/artikels/Artikels%20Gitte/Artikels/Reviews/Heck%20reactie%20Beletskaya%20%20Chem.%20Rev.%20003009.pdf

The heck reaction as a sharpening stone of palladium catalysis.

Interest in catalysis by metal nanoparticles (NPs) is increasing dramatically, as reflected by the large number of publications in the last five years. This field, "semi-heterogeneous catalysis", is at the frontier between homogeneous and heterogeneous catalysis, and progress has been made in the efficiency and selectivity of reactions and recovery and recyclability of the catalytic materials. Usually NP catalysts are prepared from a metal salt, a reducing agent, and a stabilizer and are supported on an oxide, charcoal, or a zeolite. Besides the polymers and oxides that used to be employed as standard, innovative stabilizers, media, and supports have appeared, such as dendrimers, specific ligands, ionic liquids, surfactants, membranes, carbon nanotubes, and a variety of oxides. Ligand-free procedures have provided remarkable results with extremely low metal loading. The Review presents the recent developments and the use of NP catalysis in organic synthesis, for example, in hydrogenation and C--C coupling reactions, and the heterogeneous oxidation of CO on gold NPs.

Nanoparticles as Recyclable Catalysts: The Frontier between Homogeneous and Heterogeneous Catalysis

In studying the evolution of organic chemistry and grasping its essence, one comes quickly to the conclusion that no other type of reaction plays as large a role in shaping this domain of science than carbon-carbon bond-forming reactions. The Grignard, Diels-Alder, and Wittig reactions are but three prominent examples of such processes, and are among those which have undeniably exercised decisive roles in the last century in the emergence of chemical synthesis as we know it today. In the last quarter of the 20th century, a new family of carbon-carbon bond-forming reactions based on transition-metal catalysts evolved as powerful tools in synthesis. Among them, the palladium-catalyzed cross-coupling reactions are the most prominent. In this Review, highlights of a number of selected syntheses are discussed. The examples chosen demonstrate the enormous power of these processes in the art of total synthesis and underscore their future potential in chemical synthesis.

Palladium-catalyzed cross-coupling reactions in total synthesis.

In 2010, Richard Heck, Ei-ichi Negishi, and Akira Suzuki joined the prestigious circle of Nobel Laureate chemists for their roles in discovering and developing highly practical methodologies for C-C bond construction. From their original contributions in the early 1970s the landscape of the strategies and methods of organic synthesis irreversibly changed for the modern chemist, both in academia and in industry. In this Review, we attempt to trace the historical origin of these powerful reactions, and outline the developments from the seminal discoveries leading to their eminent position as appreciated and applied today.

Palladium-Catalyzed Cross-Coupling: A Historical Contextual Perspective to the 2010 Nobel Prize

The direct functionalization of heterocyclic compounds has emerged as one of the most important topics in the field of metal-catalyzed C–H bond activation due to the fact that products are an important synthetic motif in organic synthesis, the pharmaceutical industry, and materials science. This critical review covers the recent progresses on the regioselective dehydrogenative direct coupling reaction of heteroarenes, including arylation, olefination, alkynylation, and amination/amidation mainly utilizing transition metal catalysts (113 references).

Recent advances in the transition metal-catalyzed twofold oxidative C–H bond activation strategy for C–C and C–N bond formation

Arylation of Olefin with Aryl Iodide Catalyzed by Palladium

Arylation of propylene, ethylene, styrene, and methyl acrylate with iodobenzene was found to be catalyzed by metallic palladium in methanol to give methylstyrene, styrene, t-stilbene, and methyl cinnamate, respectively. Their yields and selectivities increased significantly by the addition of excess potassium acetate as an acceptor of hydriodic acid formed. The course of catalytic reaction is discussed in terms of the oxidative addition of iodobenzene to a palladium complex of low oxidation state.

Arylation of Olefin with Iodobenzene Catalyzed by Palladium

The effect of iodide ion was examined in methanol carbonylation with use of Co-, Rh-, and Ir-catalysts. Sodium iodide gives no noticeable effect on carbonylation catalyzed by Rh-catalyst to give acetic acid, and retards that catalyzed by Ir-catalyst. Methyl iodide is effective for methanol carbonylation with Co-catalyst in the presence of hydrogen to give mainly acetaldehyde, which is readily hydrogenated to ethanol during the course of carbonylation on addition of a catalytic amount of Ru3(CO)12. Sodium iodide is also effective for acetaldehyde formation, although it strongly retards the hydrogenation of acetaldehyde with Ru-catalyst. The different effect of iodide ion on methanol carbonylation catalyzed by Co-, Rh-, or Ir-catalyst is discussed in terms of neucleophilicity of the active catalyst species.

Further Study of Methanol Carbonylation Catalyzed by Cobalt, Rhodium, and Iridium Catalysts

It was found that palladium-black is a highly active catalyst for the carbonylation of iodobenzene with carbon monoxide and methanol in the presence of potassium acetate, triethylamine, or tributylamine to give methyl benzoate. The kinetic study of the carbonylation showed that the oxidative addition of iodobenzene to a palladium(0) complex is rate-determining, and that the bases affect considerably the rate-determining step.

Effect of Base on Palladium-Black Catalyzed Carbonylation of Iodobenzene

Rhodium complexes were found to be effective in catalyzing selective hydrogenation of cinnamaldehyde to cinnamyl alcohol in the presence of strongly basic amine such as triethylamine or N-methylpyrrolidine under oxo reaction conditions. The selectivity of analogous hydrogenation of aliphatic unsaturated aldehyde was poorer than that of aromatic aldehyde. When a catalytic amount of triphenylphosphine was added, the selectivity was drastically changed to exclusive formation of hydrocinnamaldehyde. In order to elucidate the nature of rhodiumamine interaction, Rh2Cl2(CO4) was immobilized on a cross-linked chloromethylated polystyrene which was functionalized with pyrrolidine, the polymer amine acting as a tertiary amine. The polymer–rhodium complex was found to be stable and to effect the selective hydrogenation of cinnamaldehyde, while addition of triphenylphosphine seemed to liberate the rhodium complex from the polymer. It is concluded that a rhodium–amine–carbonyl complex is responsible for the selective ...

Tsutomu Mizoroki

Papers

Arylation of Olefin with Aryl Iodide Catalyzed by Palladium

Arylation of Olefin with Iodobenzene Catalyzed by Palladium

Further Study of Methanol Carbonylation Catalyzed by Cobalt, Rhodium, and Iridium Catalysts

Effect of Base on Palladium-Black Catalyzed Carbonylation of Iodobenzene

Rhodium Complex Catalyzed Hydrogenation of α,β-Unsaturated Aldehydes to Unsaturated Alcohols