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Incompatible catalytic systems

Polymer supported catalysts have advantages because of the ease of catalyst recovery and the opportunity for simultaneously using otherwise incompatible catalytic systems. Indeed, the immobilization of several catalysts onto a polymer matrix is a unique way of avoiding antagonistic reactions between them, and of lowing reagents to participate in a cascade of reactive processes. For example, polymer-supported catalysts have been used as the Lewis acid catalysts in the carbocationic polymerization of isobutylene. After the reaction, polyisobutylene is obtained by simply filtering the supported catalyst. The reaction cycle can be repeated many times. [Pg.11]

Racemization can be achieved with a variety of homogeneous catalysts. The Noyori type Ru-racemization catalyst 1 was first selected as a suitable candidate (Figure 11.3b). In fact, this was the first example in which DKR was combined with an enzyme-catalyzed polymerization reaction. It appeared, however, that polymerization with the Novozym 435/1 catalytic system was problematic only oligomers were obtained in two-step reactions because the catalysts were incompatible under the reaction conditions employed. [Pg.294]

The aryl amination protocol described previously was found to be incompatible with the formation of N-aryl heterocycles such as N-arylindoles. The electron richness of heteroaromatic substrates limits the applicability of N-arylation of indoles to more reactive aryl iodides and bromides. However, good results were obtained in coupling a number of aryl bromides and indole derivatives employing a Pd(OAc)2/SIPr HCl/NaOH catalytic system. This protocol additionally overcomes a common problem in indole synthesis, namely the formation of C-arylation side products (Scheme 23). [Pg.261]

Here, we wish to show why the task of designing a common catalytic system for the Mizoroki-Heck reaction is doomed from the beginning, because there are several largely incompatible types of catalytic process unified under this general name. This chapter is a rather impudent effort to bring at least some order into the realm of mysterious cocktails [3] published in their scores each month as novel catalytic systems for Mizoroki-Heck reactions. If there have already been so many, how could it be that problems still persist ... [Pg.52]

The understanding of the reaction mechanism appears quite difficult, owing to the complexity of the catalytic system. It is, for example, rather curious that an additive car-bonylation is obtained in spite of the oxidative conditions employed. Mechanism I (Scheme 11), however, is not incompatible with the experimental results. The reaction of but-2-en-l-ol to give 3-methylfuran-2-one was also made enantioselective (ee up to 61%) by adding poly-L-leucine as nonracemic ligand. It is worth noting that in this case a Pd—H intermediate has been proposed as the most likely intermediate, according to Mechanism IV, path h (Scheme 11). ... [Pg.972]

Two C-C Bond-Forming Events In 2008, Frechet and coworkers described an impressive asymmetric cascade reaction promoted by soluble star polymers with core-confined catalytic entities [10]. The encapsulation of catalysts into soluble star polymers allowed the use of incompatible catalysts and prevented undesired interactions between these catalytic systems. The organocascade corresponded to a nucleophilic addition of Af-methylindole to a,p-unsaturated aldehydes followed by a Michael addition of the adduct to methylvinylketone (MVK) in the presence of H-bonding additive (Scheme 12.5). Each catalyst - imidazolidinone 8 for the nucleophilic addition and diphenylprolinol methyl ether 9 for the Michael addition - or their combination cannot mediate both reaction steps. In particular, p-toluenesulfonic acid (p-TSA) diminished the ability of the chiral pyrrolidine 9 to effect enamine activation. Therefore, p-TSA and 9 were encapsulated in the core of star polymers, which cannot penetrate each other. Imidazolidone 8 was added to the acid star polymer and diffused to the core to form the salt, which allowed the iminium activation and catalyzed the first step. The second step was catalyzed by the pyrrolidine star polymer in presence of the H-bonding additive 10, which... [Pg.343]

However, despite some remarkable advances, only few of the known methods are capable of offering an economic and practical oxidation toward a particular industrially important transformation. Many of the found catalytic systems suffer from high reagent cost, instability, employment of hazardous metals or oxidants, harsh reaction conditions, operational complexity, functional group incompatibility, or production of unprocessable wastes.Thus, there is a continuing demand for new catalytic systems that could overcome such challenges. [Pg.94]

One limitation of this methodology is that unprotected terminal alkynes are incompatible with the strongly basic ethyl zinc reagents required for this reaction. Iivinghouse and coworkers found that a similar Ti(IV)tetra-aryloxide/cyclohexylmagnesium chloride system catalytically cycloisomer-ized dienes to methylenecyclopentanes 63 with the formation of some reduced product 64 (Eq. 8) [35]. [Pg.229]

The (TPP)Rh system efficiently mediates all steps, but the system is not capable of mediating the anti-Markovnikov hydro-functionalization reactions in a one-pot catalytic reaction. So far, the reaction conditions required for the different reaction steps proved incompatible. [Pg.311]

Water is likely to be present in aU practically relevant catalytic applications unless extreme precautions are taken or the system is self-drying (e.g., due to the fact that strong Lewis-acids or metal alkyls are used as co-catalysts). Water will influence the ionic liquid s thermal stability significantly if any part of the ionic liquid is prone to hydrolysis. Apart from the weU-known hydrolysis lability of tetrafluoroborates and hexafluorophosphates, water will thus also affect the stability of ester functionalities in the ionic liquid, e.g. the stability of alkyl sulfate anions. The presence of Bronsted acidity in the reaction system will further promote this kind of thermally induced hydrolysis reaction. Additionally, in strong Lewis-acidic ionic liquids care has to be taken to avoid incompatibilities between oxygen and nitrogen functionalities in the reactants or impurities and the ionic liquid s Lewis acidic group (usually a complex anion). It is for example obvious that the Pd-catalyzed dimerization of methylacrylate caimot be carried out in acidic chloroaluminate ionic hquids since the ionic liquid s anion would decompose in an irreversible reaction with the substrate methylacrylate. [Pg.450]

The electrode in Figure 23-13a is a glass electrode that responds to the ammonium ion formed by the reaction shown in the upper part of Equation 23-23. The electrode in Figure 23-13b is an ammonia gas probe that responds to the molecular ammonia in equilibrium with the ammonium ion. Unfortunately, both electrodes have limitations. The glass electrode responds to all monovalent cations, and its selectivity coefficients for NHi over Na and are such that interference occurs in most biological media (such as blood). The ammonia gas probe has a different problem — the pH of the probe is incompatible with the enzyme. The enzyme requires a pH of about 7 for maximum catalytic activity, but the sensor s maximum response occurs at a pH that is greater than 8 to 9 (where essentially all of the NH4 has been converted to NH3). Thus, the sensitivity of the electrode is limited. Both limitations are overcome by use of a fixed-bed enzyme system where the sample at a pH of about 7 is pumped over the enzyme. The resulting solution is then made alkaline and the liberated ammonia determined with an ammonia gas probe. Automated instruments (see Chapter 33) based on this technique have been on the market for several years. [Pg.348]


See other pages where Incompatible catalytic systems is mentioned: [Pg.1054]    [Pg.1413]    [Pg.1054]    [Pg.1054]    [Pg.1413]    [Pg.1054]    [Pg.142]    [Pg.948]    [Pg.186]    [Pg.364]    [Pg.394]    [Pg.415]    [Pg.1]    [Pg.197]    [Pg.529]    [Pg.82]    [Pg.367]    [Pg.495]    [Pg.404]    [Pg.701]    [Pg.680]    [Pg.385]    [Pg.404]    [Pg.203]    [Pg.94]    [Pg.195]   
See also in sourсe #XX -- [ Pg.1054 ]




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