Catalysis indium

Intramolecular cyclization of tethered phenyl ketones (58 X = Br, SiMe3) show contrasting stereochemical outcomes for indium catalysis of the alkyl bromides and fluoride ion-induced reaction of the allylsilanes. The reactions thus allow complementarity in product diastereoselectivity, and the difference appears to be related to an... 

Indium catalysis has been used. Sarmah et al. [103] developed a microwave-promoted imino-Diels-Alder reaction for the synthesis of benzo[/i]quinolines using In(OTf)3 (Figure 9.13). In this case, the diversity came from the aldehyde and alkyne reagents. The yields were good. 

The use of indium in acpieous solution has been reported by Li and co-workers as a new tool in org nometallic chemistry. Recently Loh reported catalysis of the Mukaiyama-aldol reaction by indium trichloride in aqueous solution". Fie attributed the beneficial effect of water to a eg tion phenomena in connection with the high internal pressure of this solvenf This woric has been severely criticised by... 

In summary, the groups of Espenson and Loh observe catalysis of Diels-Alder reactions involving monodentate reactants by Lewis acids in water. If their observations reflect Lewis-acid catalysis, involvirg coordination and concomitant activation of the dienophile, we would conclude that Lewis-acid catalysis in water need not suffer from a limitation to chelating reactants. This conclusion contradicts our observations which have invariably stressed the importance of a chelating potential of the dienophile. Hence it was decided to investigate the effect of indium trichloride and methylrhenium trioxide under homogeneous conditions. 

Quinoline-5-sulfonic acid, 8-hydroxy-7-iodo-metal complexes absorptiometry, 1,549 Quinolinium salts in gravimetry, 1, 535 Quinolinol metal complexes color photography, 6,107 8-Quinolinol biological activity, 6, 771 gallium and indium complexes radiopharmacology, 6, 971 radionuclide complexes radiopharmacology, 6,994 8-Quinolyl sulfate hydrolysis metal catalysis, 6,465 Quinones... 

Keywords Group 13 metals (aluminum, gallium, indium, thalhum), Ambidentate ligands. Phosphorus-nitrogen bidentate ligands, Pyridyl phosphanes, Aminoiminophosphoranes, Lewis acid catalysis... 

Certain other metal ions also exhibit catalysis in aqueous solution. Two important criteria are rate of ligand exchange and the acidity of the metal hydrate. Metal hydrates that are too acidic lead to hydrolysis of the silyl enol ether, whereas slow exchange limits the ability of catalysis to compete with other processes. Indium(III) chloride is a borderline catalysts by these criteria, but nevertheless is effective. The optimum solvent is 95 5 isopropanol-water. Under these conditions, the reaction is syn selective, suggesting a cyclic TS.63... 

Among the unique features of Sc(03SCF3)3 is its ability to function as a catalyst in hydroxylic solvents. Other dienophiles, including (V-acryloyloxazolidinones, also are subject to catalysis by Sc(03SCF3)3. Indium trichloride is another Lewis acid that can act as a catalyst in aqueous solution.40... 

In 1991, Li and Chan reported the use of indium to mediate Barbier-Grignard-type reactions in water (Eq. 8.49).108 When the allylation was mediated by indium in water, the reaction went smoothly at room temperature without any promoter, whereas the use of zinc and tin usually requires acid catalysis, heat, or sonication. The mildness of the reaction conditions makes it possible to use the indium method to allylate a methyl ketone in the presence of an acid-sensitive acetal functional group (Eq. 8.50). Furthermore, the coupling of ethyl 2-(bromomethyl)acrylate with carbonyl compounds proceeds equally well under the same reaction conditions, giving ready access to various hydroxyl acids including, for example, sialic acids. 

Conventionally, organometallic chemistry and transition-metal catalysis are carried out under an inert gas atmosphere and the exclusion of moisture has been essential. In contrast, the catalytic actions of transition metals under ambient conditions of air and water have played a key role in various enzymatic reactions, which is in sharp contrast to most transition-metal-catalyzed reactions commonly used in the laboratory. Quasi-nature catalysis has now been developed using late transition metals in air and water, for instance copper-, palladium- and rhodium-catalyzed C-C bond formation, and ruthenium-catalyzed olefin isomerization, metathesis and C-H activation. Even a Grignard-type reaction could be realized in water using a bimetallic ruthenium-indium catalytic system [67]. 

Furthermore, the use of a Lewis acid promoter leads to increased stereoselectivities (Table 19, entry C)252,254. Compared to the aprotic reaction, where allyl silane was used instead of allyl bromide and indium chloride, an almost complete reversal of the diastereos-electivity was found. It was demonstrated recently that the Lewis acid catalysed allylation reaction can be carried out efficiently without any organic solvent in saturated ammonium chloride solution255. Finally, Lewis acid catalysed Mannich reactions can be carried out conveniently in mixtures of organic solvents and water. However, the exact role of the Lewis acid catalyst has not been clarified (Table 19, entry D)253. The same reaction can be carried out in pure water with catalysis by indium trichloride256. 

The reverse reaction is catalysed by copper sulphate in an ethanol/water (50 50) mixture297 298. Indium(III) chloride catalysis of Diels-Alder reactions was also reported, but the effects were poor and comparison to uncatalysed reactions was made only in a few cases299,300. A very versatile Lewis acid catalyst for such reactions is methylrhenium trioxide (MTO)300. This catalyst can be used without a solvent, in pure organic solvents like chloroform and even in pure water. While the catalyst is active in the latter two solvents (Table 22), it gives the best results in water (Table 23). 

Silyl enol ether (38), derived from D-glucose, undergoes a useful one-carbon extension by way of an asymmetric aldol reaction the conditions of the indium(ni) catalysis in water are very convenient. 

An interesting bifunctional system with a combination of In(OTf)3 and benzoyl-quinine 65 was developed in p-lactam formation reaction from ketenes and an imino ester by Lectka [Eq. (13.40)]. High diastrereo- and enantioselectivity as well as high chemical yield were produced with the bifunctional catalysis. In the absence of the Lewis acid, polymerization of the acid chloride and imino ester occurred, and product yield was moderate. It was proposed that quinine activates ketenes (generated from acyl chloride in the presence of proton sponge) as a nucleophile to generate an enolate, while indium activates the imino ester, which favors the desired addition reaction (66) ... 

Two classes of promoter have been identified for iridium catalysed carbonylation (i) transition metal carbonyls or halocarbonyls (ri) simple group 12 and 13 iodides. Increased rates of catalysis are achieved on addition of 1-10 mole equivalents (per Ir) of the promoter. An example from each class was chosen for spectroscopic study. An Inis promoter provides a relatively simple system since the main group metal does not tend to form carbonyl complexes which can interfere with the observation of iridium species by IR. In situ HP IR studies showed that an indium promoter (Inl3 Ir = 2 1) did not greatly affect the iridium speciation, with [MeIr(CO)2l3] being converted into [Ir(CO)2l4] as the batch reaction progressed, as in the absence of promoter. 

Another interesting and different type of catalysis is involved in the catalyzed reconstruction of an indium oxide overlayer on indium. This study was alluded to earlier in the discussion of acetate ion species formed on indium oxide by chemisorption from several torr of acetic acid gas. At low partial pressures of acetic acid (<< 0.1 torr) the reversible adsorption of acetic acid catalyzes the reconstruction of a thin ( 10-15A), porous indium oxide overlayer to a defect-free (no pin holes) film as judged by pinhole sensitive tunnel junction measurements. Some clues as to the mechanism were obtained from IR plus Auger and electron loss spectroscopy as well as ellipsometry measurements. The overall process is shown in Fig. 8. This is an example where processes in the substrate themselves can be usefully catalyzed. 

Liquid injection molding, for silicone rubbers, 3, 674—675 Liquid ligands, in metal vapor synthesis, 1, 229 Liquid-phase catalysis, supported, for green olefin hydroformylation, 12, 855 Lithiacarbaboranes, preparation, 3, 114 Lithiation, arene chromium tricarbonyls, 5, 236 Lithium aluminum amides, reactions, 3, 282 Lithium aluminum hydride, for alcohol reductions, 3, 279 Lithium borohydride, in hydroborations, 9, 158 Lithium gallium hydride, in reduction reactions, 9, 738 Lithium indium hydride, in carbonyl reductions, 9, 713—714... 

Condensation reactions remain popular for the synthesis of quinolines <2006JOC6592>. Some modern variations on these classic reactions include an example of a solventless system, and the use of indium(m) chloride on silica gel under microwave conditions (Equation 160) <2003T813>. These fast, clean, high-yielding reactions gave aromatized products under indium(m) catalysis after a typical Michael addition of aniline to vinyl ketone. 

R. S. Dickson, Homogeneous Catalysis with Compounds of Rhodium and Indium, Reidel, Dordrecht, The Netherlands, 1985. 

The transmetalation of organotin derivatives to their indium counterparts (Scheme 1) has recently been used to investigate a new route to Group 13 polyfunctional Lewis acids, which are becoming important in catalysis, molecular recognition, and materials synthesis. ... 

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