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.

4.3. Reaction Mechanism 2373 4.4. Asymmetric Synthesis 2374 4.5. Outlook 2374 5. Alternating Polymerization of Oxiranes and CO2 2374 5.1. Reaction Outlines 2374 5.2. Catalyst 2376 5.3. Asymmetric Polymerization 2377 5.4. Immobilized Catalysts 2377 6. Synthesis of Urea and Urethane Derivatives 2378 7. Synthesis of Carboxylic Acid 2379 8. Synthesis of Esters and Lactones 2380 9. Synthesis of Isocyanates 2382 10. Hydrogenation and Hydroformylation, and Alcohol Homologation 2382

Transformation of carbon dioxide.

N-Heterocyclic Carbenes in Late Transition Metal Catalysis

1. Setting the Scope of the Challenge 6474 1.1. The Need for Solar Energy Supply and Storage 6474 1.2. An Imperative for Discovery Research 6477 1.3. Scope of Review 6478 2. Large-Scale Centralized Energy Storage 6478 2.1. Pumped Hydroelectric Energy Storage (PHES) 6479 2.2. Compressed Air Energy Storage (CAES) 6480 3. Smaller Scale Grid and Distributed Energy Storage 6481 3.1. Flywheel Energy Storage (FES) 6481 3.2. Superconducting Magnetic Energy Storage 6482 4. Chemical Energy Storage: Electrochemical 6482 4.1. Batteries 6482 4.1.1. Lead-Acid Batteries 6483 4.1.2. Alkaline Batteries 6484 4.1.3. Lithium-Ion Batteries 6484 4.1.4. High-Temperature Sodium Batteries 6484 4.1.5. Liquid Flow Batteries 6485 4.1.6. Metal-Air Batteries 6485 4.2. Capacitors 6485 5. Chemical Energy Storage: Solar Fuels 6486 5.1. Solar Fuels in Nature 6486 5.2. Artificial Photosynthesis and General Considerations of Water Splitting 6486

Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds

Homochiral Metal–Organic Frameworks for Asymmetric Heterogeneous Catalysis

Asymmetric Transfer Hydrogenation of Aromatic Ketones Catalyzed by Chiral Ruthenium(II) Complexes

Recent development of conceptually new chiral bifunctional transition metal based catalysts for asymmetric reductive transformations is described. The chiral bifunctional molecular catalyst promoted reduction is now realized to be a powerful tool to access chiral compounds in organic synthetic procedures in both academia and industry. Based on structural investigation of the actual catalyst and its intermediates and a deep understanding of the reaction mechanism, this asymmetric reduction system can be widely used to produce valuable chiral alcohols and is now is applicable to commercial scale production.

Asymmetric transfer hydrogenation of ketones with bifunctional transition metal-based molecular catalysts.

Carbon dioxide (CO{sub 2}) is of the greatest interest as a C{sub 1} feedstock because of the vast amounts of carbon which exist in this form and because of the low cost of bulk CO{sub 2}. Currently, toxic carbon monoxide, the main competitor for many processes, is used in industry instead because CO{sub 2} is perceived to be less reactive and its efficient catalytic conversion has remained elusive. Because CO{sub 2} is a highly oxidized, thermodynamically stable compound, its utilization requires reaction with certain high energy substances or electroreductive processes. Catalytic hydrogenation is one of the most promising approaches to CO{sub 2} fixation. Recent research has shown that high catalytic efficiency, yields, and rates of reaction can be obtained from CO{sub 2} with optimum conditions and catalysts. This review will describe the simplest and most studied reactions of CO{sub 2}: the catalytic reactions with H{sub 2} in the presence or absence of other reactive species. The mechanisms of homogeneously catalyzed reactions will be emphasized. Subjects which will not be covered, aside from brief mentions, include stoichiometric reactions of CO{sub 2} with complexes, the reverse water gas shift reaction, hydrosilylation, and electrochemical or photochemical reductions of CO{sub 2}. 132 refs.

Homogeneous Hydrogenation of Carbon Dioxide

Supercritical fluids (SCFs), compounds heated and pressurized beyond the critical point, have many unusual properties. Homogeneous molecular catalysts, which have far greater control over selectivity than heterogeneous solid catalysts, are now being tested in SCFs, and early results show that high rates, improved selectivity, and elimination of masstransfer problems can be achieved. As industry moves away from toxic or environmentally damaging solvents, supercritical carbon dioxide may be an ideal replacement medium for nonpolar or weakly polar chemical processes. More than simply substitutes for nonpolar solvents, SCFs can radically change the observed chemistry. Supercritical carbon dioxide is also an excellent medium for its own fixation, as demonstrated by studies of its hydrogenation.

Homogeneous Catalysis in Supercritical Fluids.

The discovery and development of conceptually new chiral bifunctional transition metal-based catalysts for asymmetric reactions is described. The chiral bifunctional Ru catalyst was originally developed for asymmetric transfer hydrogenation of ketones and imines and is now successfully applicable to enantioselective C–C bond formation reaction with a wide scope and high practicability. The deprotonation of 1,3-dicarbonyl compounds with the chiral amido Ru complexes leading to the amine Ru complexes bearing C- or O-bonded enolates, followed by further reactions with electrophlies gives C–C bond formation products. The present bifunctional Ru catalyst offers a great opportunity to open up new fundamentals for stereoselective molecular transformation including enantioselective C–H and C–C as well as C–O, C–N bond formation.

/pdf/bifunctional-transition-metal-based-molecular-catalysts-for-31w8yv47gb.pdf

Takao Ikariya

Papers

Asymmetric Transfer Hydrogenation of Aromatic Ketones Catalyzed by Chiral Ruthenium(II) Complexes

Asymmetric transfer hydrogenation of ketones with bifunctional transition metal-based molecular catalysts.

Homogeneous Hydrogenation of Carbon Dioxide

Homogeneous Catalysis in Supercritical Fluids.

Bifunctional transition metal-based molecular catalysts for asymmetric syntheses.