For economical and ecological reasons, synthetic chemists are confronted with the increasing obligation of optimizing their synthetic methods. Maximizing efficiency and minimizing costs in the production of molecules and macromolecules constitutes, therefore, one of the most exciting challenges of synthetic chemistry.1-3 The ideal synthesis should produce the desired product in 100% yield and selectivity, in a safe and environmentally acceptable process.4 It is now well recognized that organometallic homogeneous catalysis offers one of the most promising approaches for solving this basic problem.2 Indeed, many of these homogeneous processes occur in high yields and selectivities and under mild reaction conditions. Most importantly, the steric and electronic properties of these catalysts can be tuned by varying the metal center and/or the ligands, thus rendering tailor-made molecular and macromolecular structures accessible.5,6 Despite the fact that various efficient methods, based on organometallic homogeneous catalysis, have been developed over the last 30 years on the laboratory scale, the industrial use of homogeneous catalytic processes is relatively limited.7 The separation of the products from the reaction mixture, the recovery of the catalysts, and the need for organic solvents are the major disadvantages in the homogeneous catalytic process. For these reasons, many homogeneous processes are not used on an industrial scale despite their benefits. Among the various approaches to address these problems, liquidliquid biphasic catalysis (“biphasic catalysis”) has emerged as one of the most important alternatives.6-11 The concept of this system implies that the molecular catalyst is soluble in only one phase whereas the substrates/products remain in the other phase. The reaction can take place in one (or both) of the phases or at the interface. In most cases, the catalyst phase can be reused and the products/substrates are simply removed from the reaction mixture by decantation. Moreover, in these biphasic systems it is possible to extract the primary products during the reaction and thus modulate the product selectivity.12 For a detailed discussion about this and other concepts of homogeneous catalyst immobilization, the reader is referred elsewhere.6,7 These biphasic systems might combine the advantages of both homogeneous (greater catalyst efficiency and mild reaction conditions) and heterogeneous (ease of catalyst recycling and separation of the products) catalysis. The advent of water-soluble organometallic complexes, especially those based on sulfonated phosphorus-containing ligands, has enabled various biphasic catalytic reactions to be conducted on an industrial scale.13-15 However, the use of water as a * Corresponding author. Fax: ++ 55 51 3316 73 04. E-mail: dupont@iq.ufrgs.br. 3667 Chem. Rev. 2002, 102, 3667−3692

https://www.chem.ccu.edu.tw/~joyce/referance/gump/IL/Chem.%20Rev.%202002,%20102,%203667.pdf

Ionic liquid (molten salt) phase organometallic catalysis.

/pdf/aryl-aryl-bond-formation-one-century-after-the-discovery-of-1jdyxlkwix.pdf

Aryl-aryl bond formation one century after the discovery of the Ullmann reaction.

Efficient and reliable amplification of chirality has borne its greatest fruit with transition metal-catalyzed reactions since enantiocontrol may often be imposed by replacing an achiral or chiral racemic ligand with one that is chiral and scalemic While the most thoroughly developed enantioselective transition metal-catalyzed reactions are those involving transfer of oxygen (epoxidation and dihydroxylation)1,2 and molecular hydrogen,3 the focus of this review is on the area of enantioselective transition metal-catalyzed allylic alkylations which may involve C-C as well as C-X (X ) H or heteroatom) bond formation4-9 The synthetic utility of transitionmetal-catalyzed allylic alkylations has been soundly demonstrated since its introduction nearly three decades ago10-21 In contrast to processes where the allyl moiety acts as the nucleophilic partner, we will limit our discussion to processes which result in nucleophilic displacements on allylic substrates (eq 1) Such reactions have been recorded with a broad

http://web4.uwindsor.ca/users/j/jlichaa/reference.nsf/0/10ff8b04ff3a317885256d88005720f6/$FILE/cr-1996-96-395-allylpd-asym.pdf

Asymmetric Transition Metal-Catalyzed Allylic Alkylations.

4.2.8. Reductive Coupling 3109 5. Reaction of Aromatic Compounds 3110 5.1. Electrophilic Substitutions 3110 5.2. Radical Substitution 3111 5.3. Oxidative Coupling 3111 5.4. Photochemical Reactions 3111 6. Reaction of Carbonyl Compounds 3111 6.1. Nucleophilic Additions 3111 6.1.1. Allylation 3111 6.1.2. Propargylation 3120 6.1.3. Benzylation 3121 6.1.4. Arylation/Vinylation 3121 6.1.5. Alkynylation 3121 6.1.6. Alkylation 3121 6.1.7. Reformatsky-Type Reaction 3122 6.1.8. Direct Aldol Reaction 3122 6.1.9. Mukaiyama Aldol Reaction 3124 6.1.10. Hydrogen Cyanide Addition 3125 6.2. Pinacol Coupling 3126 6.3. Wittig Reactions 3126 7. Reaction of R,â-Unsaturated Carbonyl Compounds 3127

Organic Reactions in Aqueous Media with a Focus on Carbon−Carbon Bond Formations: A Decade Update

4.4. Pd on Modified Silica 159 4.5. Pd on Clay and Other Inorganic Materials 159 5. Stille, Fukuyama, and Negishi Reactions 159 5.1. Stille Reactions 159 5.1.1. Pd on Carbon (Pd/C) 159 5.1.2. Palladium on KF/Al2O3 159 5.1.3. Pd on Modified Silica (SiO2/TEG/Pd) 159 5.2. Fukuyama Reactions 159 5.2.1. Pd on Carbon (Pd/C) 159 5.2.2. Pd(OH)2 on Carbon (Perlman’s Catalyst) 160 5.3. Pd/C-Catalyzed Negishi Reactions 160 6. Ullmann-Type Coupling Reactions 161 6.1. Pd/C-Catalyzed Aryl−Aryl Coupling 161 6.2. Pd/C-Catalyzed Homocoupling of Vinyl Halides 162

https://www.chem.ccu.edu.tw/~joyce/referance/ericyang/Chem.%20Rev/Chem.%20Rev.%202007,%20107,%20133-173.pdf

Carbon-Carbon Coupling Reactions Catalyzed by Heterogeneous Palladium Catalysts

The contribution reviews the application of heterogeneous Pd catalysts for the manufacture of fine chemicals with special emphasis of their organic synthetic potential. In a first part, some background is given on the scope and limitations of homogeneous and heterogeneous catalysis and on significant parameters and the various types of supported Pd catalysts. Then, the application of supported Pd catalysts for important classes of transformations are reviewed organized according to reaction type. The general statements are illustrated with relevant examples from the literature and from our own laboratories. Hydrogenation, hydrogenolysis, and dehydrogenation reactions are considered to be mature technologies with an extremely broad scope both for small-scale laboratory applications and large to very large-scale manufacturing processes. Oxidation reactions and CC coupling reactions usually have a rather narrow scope and only relatively few have been developed to the technical stage. Especially for CC coupling reactions, the nature of the active Pd species is under debate because it is not clear whether the reaction takes place on the metallic surface or whether leached soluble Pd complexes are the active catalysts.

Supported palladium catalysts for fine chemicals synthesis

RD ii) finding shorter routes to target molecules using catalytic methods; iii) development of industrial catalytic processes in multi-step syntheses.

Industrial R&D on Catalytic CC and CN Coupling Reactions: A Personal Account on Goals, Approaches and Results

Suzuki-type coupling of chloroarenes with arylboronic acids catalysed by nickel complexes

A new generation of air stable, highly active Pd complexes for C--C and C--N coupling reactions with aryl chlorides.

The right ligand enables the efficient carbonylation of unactivated chloroarenes. A general synthesis of benzoic acid derivatives is possible with the palladium-ferrocenylphosphane catalysts.

Adriano Indolese

Papers

Supported palladium catalysts for fine chemicals synthesis

Industrial R&D on Catalytic CC and CN Coupling Reactions: A Personal Account on Goals, Approaches and Results

Suzuki-type coupling of chloroarenes with arylboronic acids catalysed by nickel complexes

A new generation of air stable, highly active Pd complexes for C--C and C--N coupling reactions with aryl chlorides.

A More Efficient Catalyst for the Carbonylation of Chloroarenes