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

Palladium-catalyzed vinylic hydrogen substitution reactions with aryl, benzyl, and styryl halides

Palladium-catalyzed reactions of organic halides with olefins

Acylation, methylation, and carboxyalkylation of olefins by Group VIII metal derivatives

The Reaction of Cobalt Hydrotetracarbonyl with Olefins

The palladium-catalyzed vinylation of organic halides provides a very convenient method for forming carboncarbon bonds at unsubstituted vinylic positions. Generally the reaction does not require anhydrous or anaerobic conditions although it is advisable to limit access of oxygen when arylphosphines are used as a component of the catalyst. The transformation is valuable because it cannot be carried out in a single step by any other known method (except in certain Meerwein reactions).



The organic halide employed is limited to aryl, heterocyclic, benzyl, or vinyl types, with bromides and iodides seen most often. Halides with an easily eliminated beta-hydrogen atom (i.e., alkyl derivatives) cannot be used since they form only olefins by elimination under the normal reaction conditions. The base needed may be a secondary or tertiary amine, sodium or potassium acetate, carbonate, or bicarbonate.



When nucleophilic secondary amines are used as coreactants with most vinylic halides, a variation occurs that often produces tertiary allylic amines as major products. The catalyst is commonly palladium acetate, although palladium chloride or preformed triarylphosphine palladium complexes, as well as palladium on charcoal, have been used. A reactant, product, or solvent may serve as the ligand in reactions involving organic iodides, but generally a triarylphosphine or a secondary amine is required when organic bromides are used. The reaction, which occurs between ca. 50° and 160° proceeds homogeneously. Solvents such as acetonitrile, dimethylformamide, hexamethylphosphoramide, N-methylpyrrolidinone, and methanol have been used, but are often not necessary. The procedure is applicable to a very wide range of reactants and yields are generally good to excellent.



Several variations of the reaction are known in which the organic halide is replaced by other reagents such as organometallics, diazonium salts, or aromatic hydrocarbons. These reactions are not discussed in detail, but are only briefly compared with the halide reaction. Other related reactions such as the palladium-catalyzed replacement of allylic substituents with carbanionic reagents, the palladium-promoted nucleophilic substitutions at olefinic carbons, and the numerous palladium-catalyzed coupling reactions of halides and organometallics are also beyond the scope of this review. The palladium-catalyzed vinylic substitution reaction has not yet received much attention from organic chemists, but its broad scope and simplicity demonstrate that it is a useful method for the synthesis of a variety of olefinic compounds.


Keywords:

palladium catalyst;
vinylation;
organic halides;
scope;
limitations;
experimental procedures;
vinylic substitution;
ethylene;
acrylic acid;
butenol;
methyl acrylate;
styrene;
pentadiene;
acrolein dimethyl acetal;
olefins

Richard F. Heck

Papers

Palladium-catalyzed vinylic hydrogen substitution reactions with aryl, benzyl, and styryl halides

Palladium-catalyzed reactions of organic halides with olefins

Acylation, methylation, and carboxyalkylation of olefins by Group VIII metal derivatives

The Reaction of Cobalt Hydrotetracarbonyl with Olefins

Palladium‐Catalyzed Vinylation of Organic Halides