In the investigation of efficient chemical transformations, the carbon-carbon bond-forming reactions play an outstanding role. In this context, organocatalytic processes have achieved considerable attention. 1 Beside their facile reaction course, selectivity, and environmental friendliness, new synthetic strategies are made possible. Particularly, the inversion of the classical reactivity (Umpolung) opens up new synthetic pathways. 2 In nature, the coenzyme thiamine (vitamin B1), a natural thiazolium salt, utilizes a catalytic variant of this concept in biochemical processes as nucleophilic acylations. 3 The catalytically active species is a nucleophilic carbene. 4

Organocatalysis by N-Heterocyclic Carbenes

Photoinduced motions in azo-containing polymers.

Polymer brushes: surface-immobilized macromolecules

The interaction of polymers with their environment depends largely on the functional groups they carry. Interfaces between different polymers or between polymers and other surfaces can be strengthened through the design of molecular interactions such as hydrogen bonding and through the control of polymer architecture. The placement of functional groups at polymer chain ends or in well-defined segments can determine the ultimate properties. Three-dimensional synthetic polymers such as dendrimers can be fashioned to encapsulate reactive sites or provide highly controlled surfaces and interfaces.

http://science.sciencemag.org/content/sci/263/5154/1710.full.pdf

Functional polymers and dendrimers: reactivity, molecular architecture, and interfacial energy

The chemistry of copper is extremely rich because it can easily access Cu0, CuI, CuII, and CuIII oxidation states allowing it to act through one-electron or two-electron processes. As a result, both radical pathways and powerful two-electron bond forming pathways via organmetallic intermediates, similar to those of palladium, can occur. In addition, the different oxidation states of copper associate well with a large number of different functional groups via Lewis acid interactions or π-coordination. In total, these feature confer a remarkably broad range of activities allowing copper to catalyze the oxidation and oxidative union of many substrates.

Oxygen is a highly atom economical, environmentally benign, and abundant oxidant, which makes it ideal in many ways.1 The high activation energies in the reactions of oxygen require that catalysts be employed.2 In combination with molecular oxygen, the chemistry of copper catalysis increases exponentially since oxygen can act as either a sink for electrons (oxidase activity) and/or as a source of oxygen atoms that are incorporated into the product (oxygenase activity). The oxidation of copper with oxygen is a facile process allowing catalytic turnover in net oxidative processes and ready access to the higher CuIII oxidation state, which enables a range of powerful transformations including two-electron reductive elimination to CuI. Molecular oxygen is also not hampered by toxic byproducts, being either reduced to water, occasionally via H2O2 (oxidase activity) or incorporated into the target structure with high atom economy (oxygenase activity). Such oxidations using oxygen or air (21% oxygen) have been employed safely in numerous commodity chemical continuous and batch processes.3

However, batch reactors employing volatile hydrocarbon solvents require that oxygen concentrations be kept low in the head space (typically <5–11%) to avoid flammable mixtures, which can limit the oxygen concentration in the reaction mixture.4,5,6 A number of alternate approaches have been developed allowing oxidation chemistry to be used safely across a broader array of conditions. For example, use of carbon dioxide instead of nitrogen as a diluent leads to reduced flammability.5 Alternately, water can be added to moderate the flammability allowing even pure oxygen to be employed.6 New reactor designs also allow pure oxygen to be used instead of diluted oxygen by maintaining gas bubbles in the solvent, which greatly improves reaction rates and prevents the build up of higher concentrations of oxygen in the head space.4a,7 Supercritical carbon dioxide has been found to be advantageous as a solvent due its chemical inertness towards oxidizing agents and its complete miscibility with oxygen or air over a wide range of temperatures.8 An number of flow technologies9 including flow reactors,10 capillary flow reactors,11 microchannel/microstructure structure reactors,12 and membrane reactors13 limit the amount of or afford separation of hydrocarbon/oxygen vapor phase thereby reducing the potential for explosions.

Enzymatic oxidizing systems based upon copper that exploit the many advantages and unique aspects of copper as a catalyst and oxygen as an oxidant as described in the preceding paragraphs are well known. They represent a powerful set of catalysts able to direct beautiful redox chemistry in a highly site-selective and stereoselective manner on simple as well as highly functionalized molecules. This ability has inspired organic chemists to discover small molecule catalysts that can emulate such processes. In addition, copper has been recognized as a powerful catalyst in several industrial processes (e.g. phenol polymerization, Glaser-Hay alkyne coupling) stimulating the study of the fundamental reaction steps and the organometallic copper intermediates. These studies have inspiried the development of nonenzymatic copper catalysts. For these reasons, the study of copper catalysis using molecular oxygen has undergone explosive growth, from 30 citations per year in the 1980s to over 300 citations per year in the 2000s.

A number of elegant reviews on the subject of catalytic copper oxidation chemistry have appeared. Most recently, reviews provide selected coverage of copper catalysts14 or a discussion of their use in the aerobic functionalization of C–H bonds.15 Other recent reviews cover copper and other metal catalysts with a range of oxidants, including oxygen, but several reaction types are not covered.16 Several other works provide a valuable overview of earlier efforts in the field.17 This review comprehensively covers copper catalyzed oxidation chemistry using oxygen as the oxidant up through 2011. Stoichiometric reactions with copper are discussed, as necessary, to put the development of the catalytic processes in context. Mixed metal systems utilizing copper, such as palladium catalyzed Wacker processes, are not included here. Decomposition reactions involving copper/oxygen and model systems of copper enzymes are not discussed exhaustively. To facilitate analysis of the reactions under discussion, the current mechanistic hypothesis is provided for each reaction. As our understanding of the basic chemical steps involving copper improve, it is expected that many of these mechanisms will evolve accordingly.

/pdf/aerobic-copper-catalyzed-organic-reactions-3ctljpvivz.pdf

Aerobic Copper-Catalyzed Organic Reactions

Influence of tacticity of poly(methyl methacrylate) on the compatibility with poly(vinylidene fluoride)

https://pure.rug.nl/ws/files/6805118/1990PolymerBoven.pdf

Grafting kinetics of poly(methyl methacrylate) on microparticulate silica

A mechanistic study of rhodium tri(o-t-butylphenyl)phosphite complexes as hydroformylation catalysts

Etude par diffractometrie RX d'une fibre de stereocomplexe montrant une structure en helice bicatenaire ayant un motif assymetrique constitue d'une unite isotactique et de 2 unites syndiotactiques. Grande tolerance de la structure aux defauts (fins de chaine, boucles). Resultats en faveur d'une complexation favorisee par une bonne adaptation sterique des 2 chaines

Complexation of stereoregular poly(methyl methacrylates) .14. the basic structure of the stereocomplex of isotactic and syndiotactic poly(methyl methacrylate)

Ab initio unrestricted Hartree−Fock calculations with a 6-31G* basis set were performed on 2,6-dimethylphenol (DMP or monomer) and 4-(2,6-dimethylphenoxy)-2,6-dimethylphenol (dimer) to gain more insight into the mechanism of the copper-catalyzed oxidative phenol coupling reaction. Atomic charges were determined for the phenol, phenoxyl radical, phenolate anion and phenoxonium cation (both the singlet and triplet state) of both species. Calculations for the monomer show that the only aromatic carbon atom bearing a partial positive atomic charge is the para carbon of the cation in the singlet state. In the case of the dimer, the presence of a p-phenoxy substituent results in a partial positive charge for the para carbon of the first aromatic ring in all states, but this charge is significantly higher for the singlet cation. In the singlet cationic state, the para carbon of the first aromatic ring is therefore the site most susceptible to nucleophilic aromatic substitution. This result strongly supports a pr...

Ab Initio Calculations on 2,6-Dimethylphenol and 4-(2,6-Dimethylphenoxy)-2,6-dimethylphenol. Evidence of an Important Role for the Phenoxonium Cation in the Copper-Catalyzed Oxidative Phenol Coupling Reaction

Ger Challa

Papers

Influence of tacticity of poly(methyl methacrylate) on the compatibility with poly(vinylidene fluoride)

Grafting kinetics of poly(methyl methacrylate) on microparticulate silica

A mechanistic study of rhodium tri(o-t-butylphenyl)phosphite complexes as hydroformylation catalysts

Complexation of stereoregular poly(methyl methacrylates) .14. the basic structure of the stereocomplex of isotactic and syndiotactic poly(methyl methacrylate)

Ab Initio Calculations on 2,6-Dimethylphenol and 4-(2,6-Dimethylphenoxy)-2,6-dimethylphenol. Evidence of an Important Role for the Phenoxonium Cation in the Copper-Catalyzed Oxidative Phenol Coupling Reaction