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Catalytic reactions after completion

Recently, Majoral et al. described the synthesis of a third-generation phosphorus-containing dendrimer possessing 24 chiral iminophosphine end groups derived from (2S)-2-amino-l-(diphenylphosphinyl)-3-methylbutane (Fig. 11) [32]. The dendritic catalyst was tested in allylic substitution reactions, using rac-(.E)-diphenyl-2-propenyl acetate or pivalate as substrates. The observed enantioselectivities were good to excellent (max. 95% ee) in all reactions. After completion of the catalytic reaction, the catalyst could be reused at least twice after precipitation and filtration. A slight decrease... [Pg.74]

This goal might well be achieved by introducing an auxiliary that aids the coordination to the catalyst. After completion of the Diels-Alder reaction and removal of the auxiliary the desired adduct is obtained. This approach is summarised in Scheme 4.6. Some examples in which a temporary additional coordination site has been introduced to aid a catalytic reaction have been reported in the literature and are described in Section 4.2.1. Section 4.2.2 relates an attempt to use (2-pyridyl)hydrazone as coordinating auxiliary for the Lewis-acid catalysed Diels-Alder reaction. [Pg.111]

The time-dependence of enantioselectivity in the reaction thiophenol with 3-cro-tonoyl-2-oxazolidinone catalyzed by l ,J -DBFOX/Ph-Ni(C104)2-3H2O at room temperature in THF is shown in Scheme 7.44. After 3 h, the yield of the thiol adduct is 70% with the enantioselectivity of 91% ee, but the enantioselectivity was 80% ee at the completion of reaction after 24 h (yield 100%). Although the catalyst maintains a high catalytic activity, and hence a satisfactory enantioselectivity, at the early stage of reaction, the deterioration of catalyst cannot be neglected thereafter even under neutral conditions. [Pg.288]

Cul, 12mol% of 2,2 -dipyridyl, in lOvol of xylene diglyme (9 1) at 140°C with azeotropic removal of the water as it was formed. The azeotropic removal of water helped alleviate the problem of solids coating the reaction vessel walls, which led to stalling of the reaction. The reaction was complete in less than lOh, typically with 96% assay yield and 92% isolated yield for 49 after aqueous work-up and subsequent crystallization [14b-d]. It was noteworthy that this catalytic system composed of the copper(I) salt with bipyridyl ligand was recently reported to be applicable to a wide range of Ullmann-type ether formations [14d]. [Pg.156]

A catalyst is a substance that increases the rate of a chemical reaction without itself being changed in the process. That is, the substance called a catalyst is the same after the reaction as before. During the reaction, it may become a different entity, but after the catalytic cycle is complete, the catalyst is the same as at the start. [Pg.2]

Unfortunately, the appeal of solid phase extractions on small scale fades as the scale increases due to the cost and inconvenience of using large amounts of fluorous silica gel. Here, modified techniques to reduce the tedium of repeated extractions are attractive. For example, Crich has recently introduced the minimally fluorous selenide C6Fi3CH2CH2C6H4SeH[171. This selenol is added in catalytic quantities to tin hydride reductions of reactive aryl and vinyl radicals. The high reducing capacity of the aryl selenide suppresses undesired reactions of product radicals without suppressing the reactions of the aryl and vinyl radicals themselves. After the reaction is complete, the selenol can be recovered by a modified continuous extraction procedure. [Pg.32]

Fig. 1 Graphical representation shows immobilized enzyme catalytic activity and their recovery after the completion of the catalytic reaction using a simple magnet. Fig. 1 Graphical representation shows immobilized enzyme catalytic activity and their recovery after the completion of the catalytic reaction using a simple magnet.
In the chemical industry, iodine and/or iodine compounds are often used as catalysts and/or catalytic promoters for the production of value-added organic chemicals. As with other catalytic reactions, the catalyst or promoter must be removed from the products after completing the reaction. However, removing trace amounts of organic iodide contaminates from the product by conventional distillation techniques is difficult primarily due to the fact that iodine compounds are unstable and split off into various boiling ranges. [Pg.190]

The soluble catalytic species was generated in situ by reaction of the polybinaphthyl resin (19) with diethylzinc prior to addition of the unsaturated ketone and tBuOOH (Scheme 4.11). After completion of the reaction, the soluble polymer had to be precipitated by addition of methanol. Yields were reported in the range between 67 to 95% [77]. [Pg.214]

In most cases the catalytically active metal complex moiety is attached to a polymer carrying tertiary phosphine units. Such phosphinated polymers can be prepared from well-known water soluble polymers such as poly(ethyleneimine), poly(acryhc acid) [90,91] or polyethers [92] (see also Chapter 2). The solubility of these catalysts is often pH-dependent [90,91,93] so they can be separated from the reaction mixture by proper manipulation of the pH. Some polymers, such as the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers, have inverse temperature dependent solubihty in water and retain this property after functionahzation with PPh2 and subsequent complexation with rhodium(I). The effect of temperature was demonstrated in the hydrogenation of aqueous allyl alcohol, which proceeded rapidly at 0 °C but stopped completely at 40 °C at which temperature the catalyst precipitated hydrogenation resumed by coohng the solution to 0 °C [92]. Such smart catalysts may have special value in regulating the rate of strongly exothermic catalytic reactions. [Pg.74]

With a catalytic amount of diisobutyi telluride method B. Chalcone (0.5 mmol), cesium carbonate (1.0 mmol), ( )-3-bromo-l-trimethylsilylprop-l-ene (0.75 mmol), diisobutyi telluride (0.1 mmol), THF (5 cm ) and water (5 mm ) were mixed in a reaction tube and stirred at 50°C for a specific period of time. After 28 h, additional trimethylsilylallyl bromide (0.25 mmol) was added and stirring continued for 20 h. When the reaction was complete (monitored by TLC), work-up as for method A and flash chromatography of the residue on silica gel afforded the product, of purity >98% (GC). [Pg.223]

In 2007, Hiemstra et al. established a catalytic asymmetric Pictet-Spengler reaction that proceeds via (V-sulfenyliminium ions (Scheme 15) [27], Treatment of iV-sulfenylated tryptamines 42 with aldehydes 40 and BINOL phosphate (R)-3f (5 mol%, R = 3,5-(CF3)2-CgH3) afforded tetrahydro-P-carbohnes. After completion of the cyclization the sulfenyl group was cleaved by the use of HCl. This one-pot... [Pg.409]

Phenylacetylene 13 readily reacts with Me2PhSiH under CO pressure to give 3-dimethylphenylsilyl-2-phenyl-propenal 14a in the presence of a catalytic amount of Rh4(CO)i2 (Equation (2)). When 10-20 atm of CO pressure and 0.1-0.2 mol% of Rh4(GO)i2 are applied, the reaction is completed within 2 h at 100 °G. Silylformylation proceeds smoothly even at room temperature, though the reaction becomes slower (600-700 turnover frequency at room temperature after 17 h). The reaction does proceed in the absence of Et3N, but its presence improves yield and (Z)-selectivity of product 14a. ... [Pg.475]

Ionic liquids have been used for the selenium- or palladium-catalyzed carbonylation of primary amines to form carbamates or ureas.After completion of the carbonylation, addition of water induced the precipitation of desired products, which were isolated by fdtration and separated from the ionic liquid, containing the catalytic species. Then, the catalyst could be reused after removal of residual methanol and water by distillation. Although the conversion of the reaction slightly decreased after the second run, the catalytic activity was considerably improved (from 70% to 99 %) by the addition of a small amount of the fresh catalyst. " ... [Pg.548]

After 4 or 5 hours the reaction is complete and a sigmoidal living ends formation curve is observed (1 ). The degree of polymerization of the oligoisoprenyllithium equals about ten. By addition of catalytic amounts of complexing agent (TMEDA or PMDT) the remarkable increase of the initiation rate is not measurable by ultra violet spectroscopy. Also, only the propagation step was studied. [Pg.465]


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After Completion

Reaction completion

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