Novel catalysis

Controlling polymer microstructure through novel catalysis and chemistry... 

S. P., Wilkinson, D. J., Parallel chemistry investigations of ortho-directed hydrogen isotope exchange between substituted aromatics and isotopic water novel catalysis by cyclooctadienyliridium( I) pentan-1,3-dionates, Tetrahedron Lett. 2000, 41, 2705-2708. 

Aromatics for oxidative polymerization usually show high oxidation potentials. The direct oxidation of these monomers by 02 does not proceed because of the large potential gap between the monomers and 02. A novel catalysis by vanadyl complexes is applicable to the synthesis of PPS by the 02-oxidative polymerization of diphenyl disulfide (Eq. 10) [93-103], In the presence of VO(acac)2, the polymerization is accompanied by a quantitative 02 uptake. Dioxygen is essential for the VO-catalyzed oxidative polymerization of diphenyl disulfide. 

As mentioned earlier (Section 1.5) another example of novel catalysis in an aqueous medium is the use of lanthanide triflates as water-tolerant Lewis acid catalysts for a variety of organic transformations in water [39]. 

As another example of novel catalysis employing montmorillonite, the clay was found to show excellent catalytic activity for the addition reaction of trimethylsilyl ketene acetal to a, -acetylenic esters (ynoates), which contrasted strikingly with the reactions induced by a homogeneous acid catalyst, trimethylsilyl triflate (TMSOTf), as well as the addition reactions of lithium enolates with ynoates [Eq. (17)] (89). Table XXIII summarizes the results of the reactions of the silicon and lithium enolates of methyl propionate (21) with ynoates (22a-c). Except for the reaction of 22c, ferric ion-exchanged montmorillonite (Fe-Mont), which is more acidic than Al-Mont, catalyzed exclusive 1,2-additions of trimethylsilyl ketene acetal to 22a and 22b to give 23 in... 

Novel Catalysis Technology A Case Study - the Albene Process, keynote lecture, d World Chemical Engineering Congress, Karlsruhe, Germany, June 1991. 

This interpretation is supported by extension of this novel catalysis to cyclic olefins (32, 32a). Cyclic olefins undergo smooth ring-opening polymerization to polymers which are, in fact, massive ring polyenes of structure XVIII. 

Very recently, Zhu and coworkers have developed a novel catalysis that was applicable to the reaction of acrylate with both aromatic and aliphatic imines [21]. The 6 OH group in p ICD provided a handle for the introduction of other H bond donors that were capable of modulating both the steric and electronic parameters. Consequently, a series of amides and thioureas were synthesized from [5 ICD and screened as catalysts using N (p methoxybenzenesulfonyl)imine and [5 naphthyl acrylate as model substrates. As summarized in Table 13.2, after a survey of reaction conditions by varying the solvents, the temperatures, the stoichiometries, and the... 

Elimination of toxic reagents and intermediates [via novel catalysis] ...Anhydrous hydrofluoric and fuming sulfuric acids are used as catalysts throughout the chemical and petroleum industry. Replacing these materials with safe, solid catalysts could have a profound positive impact on industry. 

Ishii, Y. (1996) A novel catalysis of JV-hydroxyphthalimide (NHPI) in the oxidation of organic substrates with molecular oxygen. 6th International Symposium on the Activation of Dioxygen and Homogeneous Catalysis, April 14-19, 1996. 

Bosch E, Rathore R, Kochi JK (1994) Novel catalysis of hydroquinone autoxidation with nitrogen oxides. J Org Chem 59 2529... 

Hartmann P, Trettnak W (1996) Effects of polymer matrixes on calibration functions of luminescent oxygen sensors based on porphyrin ketone complexes. Anal Chem 68 2615-2620 Haruta M (1997) Novel catalysis of gold deposited on metal oxides. Catal Surv Jpn 1 61-73... 

The sonochemistry of solutes dissolved in organic Hquids also remains largely unexplored. The sonochemistry of metal carbonyl compounds is an exception (57). Detailed studies of these systems led to important mechanistic understandings of the nature of sonochemistry. A variety of unusual reactivity patterns have been observed during ultrasonic irradiation, including multiple ligand dissociation, novel metal cluster formation, and the initiation of homogeneous catalysis at low ambient temperature (57). 

Catalysis. Ion implantation and sputtering in general are useful methods for preparing catalysts on metal and insulator substrates. This has been demonstrated for reactions at gas—soHd and Hquid—soHd interfaces. Ion implantation should be considered in cases where good adhesion of the active metal to the substrate is needed or production of novel materials with catalytic properties different from either the substrate or the pure active metal is wanted (129—131). Ion beam mixing of deposited films also promises interesting prospects for the preparation of catalysts (132). 

NOVEL MATERIALS FOR CATALYSIS AND ANALYSIS DERIVED FROM RENEWABLE RESOURCES... 

The development of novel materials for applications such as catalysis has been a very important area of work, with several classes of materials being developed and applied (for example, zeolites and their mesoporous analogues, hydrotalcites, hydroxyapatites, clays). 

With the discovery of the crowns and related species, it was inevitable that a search would begin for simpler and simpler relatives which might be useful in similar applications. Perhaps these compounds would be easier and more economical to prepare and ultimately, of course, better in one respect or another than the molecules which inspired the research. In particular, the collateral developments of crown ether chemistry and phase transfer catalysis fostered an interest in utilizing the readily available polyethylene glycol mono- or dimethyl ethers as catalysts for such reactions. Although there is considerable literature in this area, much of it relates to the use of simple polyethylene glycols in phase transfer processes. Since our main concern in this monograph is with novel structures, we will discuss these simple examples further only briefly, below. 

However, research into transition metal catalysis in ionic liquids should not focus only on the question of how to make some specific products more economical or ecological by use of a new solvent and, presumably, a new multiphasic process. Since it bridges the gap between homogeneous and heterogeneous catalysis, in a novel and highly attractive manner, the application of ionic liquids in transition metal catalysis gives access to some much more fundamental and conceptual questions for basic research. 

To overcome these limitations, there has been a great deal of investigation of novel methods, one of them focused on the search for alternative solvents [6, 7]. Table 5.3-1 gives different approaches to biphasic catalysis, with some of their respective advantages and limitations. 

A novel use of a chlorofluorocarbon is in the synthesis of a pyrone (30) from 1,1,1-trichlorotrifluoroethane. The key step involves Cu(I) catalysis. Pyrone (30) is a useful CF3 aromatic synthon, as it readily underwent (4 + 2) cycloaddition followed by spontaneous elimination of C02 (85-TL3947). 

This is an emerging field that has not reached its final position yet. Members of the novel class of FCP, SCP, and HAD phosphatases require Mg2+ for catalysis. An aspartate residue within the active site signature motif (DxDx(T/V)) is essential to form an acyl-phosphate intermediate. Many members of the the HAD (haloacid dehalogenase) superfamily have phosphoesterase activity [3]. Some of those protein phosphatases act on... 

The mechanistic investigations presented in this section have stimulated research directed to the development of advanced ruthenium precatalysts for olefin metathesis. It was pointed out by Grubbs et al. that the utility of a catalyst is determined by the ratio of catalysis to the rate of decomposition [31]. The decomposition of ruthenium methylidene complexes, which attribute to approximately 95% of the turnover, proceeds monomolecularly, which explains the commonly observed problem that slowly reacting substrates require high catalyst loadings [31]. This problem has been addressed by the development of a novel class of ruthenium precatalysts, the so-called second-generation catalysts. 

Enzyme-mediated oxidation reactions offer highly diverse options for the modification of existing functional groups as well as for the introduction of novel function in chiral catalysis. Biooxidations often enable us to obtain complementary solutions to metal-assisted transformations and organocatalysis and are considered one of the important strategies of green chemistry . 

Figure 10.39 Synthesis of a novel N-hydroxypyrrolidine and a fluorogenic screening substrate for transaldolases based on stereospecific transketolase catalysis.

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