Pick your Pd partners: A number of catalytic systems have been developed for palladium-catalyzed CH activation/CC bond formation. Recent studies concerning the palladium(II)-catalyzed coupling of CH bonds with organometallic reagents through a PdII/Pd0 catalytic cycle are discussed (see scheme), and the versatility and practicality of this new mode of catalysis are presented. Unaddressed questions and the potential for development in the field are also addressed.

In the past decade, palladium-catalyzed CH activation/CC bond-forming reactions have emerged as promising new catalytic transformations; however, development in this field is still at an early stage compared to the state of the art in cross-coupling reactions using aryl and alkyl halides. This Review begins with a brief introduction of four extensively investigated modes of catalysis for forming CC bonds from CH bonds: PdII/Pd0, PdII/PdIV, Pd0/PdII/PdIV, and Pd0/PdII catalysis. A more detailed discussion is then directed towards the recent development of palladium(II)-catalyzed coupling of CH bonds with organometallic reagents through a PdII/Pd0 catalytic cycle. Despite the progress made to date, improving the versatility and practicality of this new reaction remains a tremendous challenge.

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Palladium(II)-catalyzed C-H activation/C-C cross-coupling reactions: versatility and practicality.

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 Reaction of Iodine with Acylcobalt Tricarbonyl Triphenylphosphine Complexes

Carboxylic acid amides are obtained from aryl, heterocyclic, and vinylic halides and substituted derivates thereof, by reacting same with a primary or secondary amine and carbon monoxide, in the presence of a palladium catalyst and if necessry a tertiary amine at about 20°-150° C and from at least a half atmosphere pressure.

Process for the preparation of carboxylic acid amides from organic halides

Neighboring Carbon and Hydrogen. XXVIII. Ar2-6 Participation in Solvolysis of Some ι-Aryl-1-alkyl Bromobenzenesulfonates1,2

Several reactions of organopalladium compounds with potential applications in organic syntheses have been reported in recent years; however, very few of these reactions have ever actually been used to solve synthetic problems. This lack of interest is probably due to two factors: a lack of information on the reaction and a reluctance of the synthetic chemist to attempt reactions with unfamiliar reagents. Although many organometallic reactions require specialized techniques, such as very pure inert atmospheres, careful purification of reagents, precise concentration measurements, precausions for spontaneously inflammable or highly toxic reagents, and high-pressure apparatus, some palladium-catalyzed reactions do not require any of these techniques. In this paper, I will describe and summarize the available information on one of these reactions and indicate why I think it is a useful synthetic reaction. I believe the simplicity, convenience, and advantages of the reaction compared with other methods in many instances will become clear later on. The reaction is the palladium-catalyzed vinylic hydrogen substitution reaction with organic halides. The basic reaction is the following:

Richard F. Heck

Papers

The Reaction of Iodine with Acylcobalt Tricarbonyl Triphenylphosphine Complexes

Process for the preparation of carboxylic acid amides from organic halides

Neighboring Carbon and Hydrogen. XXVIII. Ar2-6 Participation in Solvolysis of Some ι-Aryl-1-alkyl Bromobenzenesulfonates1,2

Catalytic applications of palladium in organic syntheses

The Addition of Acylcobalt Carbonyls to α,β-Unsaturated Carbonyl Compounds. 1-Acyloxy-π-allylcobalt Tricarbonyl Derivatives