Indium halides

Halides. Indium trichloride [10025-83-8] InCl, can be made by heating indium in excess chlorine or by chlorinating lower chlorides. It is a white crystalline soHd, deUquescent, soluble in water, and has a high vapor pressure. InCl forms chloroindates, double salts with chlorides of alkaLi metals, and organic bases. 

Acetyl ligands, in niobium complexes, C-H BDEs, 1, 298 Achiral phosphines, on polymer-supported peptides, 12, 698 Acid halides, indium compound reactions, 9, 683 Acidity, one-electron oxidized metal hydrides, 1, 294 Acid leaching, in organometallic stability studies, 12, 612 Acid-platinum rf-monoalkynes, interactions, 8, 641 Acrylate, polymerization with aluminum catalysts, 3, 280 Acrylic monomers, lanthanide-catalyzed polymerization,... 

Again, the complete series of InYX compounds (Y = S,Se,Te X = Cl,Br,I) exists. Of the Group IIIA chalcogenide halides, the indium compounds have been the most extensively studied. 

Indium chalcogenide chlorides and bromides are obtained by heating mixtures of the chalcogenide and the halide in sealed ampoules to temperatures between 200 and 420°C (see Table XIX). For the preparation of the chalcogenide iodides. In and I2 are used instead of Inlj. InTel may be synthesized directly from the elements (161). 

The telluride halides crystallize in monoclinic lattices, but only In-TeBr and InTel are isotypic 162). InTeCl forms a layer type of structure, as do InSCl and its analogs, but, owing to the size of the Te atom and the enhanced covalency of the In-Te bond, only a coordination number of 4 for indium is realized. The structure is built up of strongly distorted, InTesraCli/j tetrahedra that share the corners and edges occupied by Te atoms. The Cl atoms are coordinated to one tetrahedron each, and do not take part in the layer formation 324, 325). 

Apart from the fluoride, mercuric halides react explosively with potassium like all analogues of the other metals already mentioned. With mercurous salts, the reaction seems less violent since with mercurous chloride, molten potassium causes the mixture to incandesce without ever combusting. It is likely that other metals react too an extreme violent reaction was mentioned between indium and mercuric bromide. 

A striking feature of the reactions of indium and allylic halides is that they can be carried out in aqueous solution.192 The aldehyde traps the organometallic intermediate as it is formed. 

Among all the nucleophilic addition reactions of carbonyl compounds, allylation reaction has been the most successful, partly due to the relatively high reactivity of allyl halides. Various metals have been found to be effective in mediating such a reaction (Scheme 8.4). Among them, indium has emerged as the most popular metal for such a reaction. 

Indium-mediated allylation of an unreactive halide with an aldehyde132 was used to synthesize an advanced intermediate in the synthesis of antillatoxin,133 a marine cyanobacteria (Lyngbya majus-cula) that is one of the most ichthyotoxic compounds isolated from a marine plant to date. In the presence of a lanthanide triflate, the indium-mediated allylation of Z-2-bromocrotyl chloride and aldehyde in saturated NH4C1 under sonication yielded the desired advanced intermediate as a 1 1 mixture of diastereomers in 70% yield. Loh et al.134 then changed the halide compound to methyl (Z)-2-(bromomethyl)-2-butenoate and coupled it with aldehyde under the same conditions to yield the desired homoallylic alcohol in 80% yield with a high 93 7 syn anti selectivity (Eq. 8.55). 

Regio- and Stereoselectivity. For the allylation of carbonyl compounds mediated by indium and other compounds in aqueous media, usually the carbon-carbon bond forms at the more substituted carbon of the allyl halide, irrespective of the position of halogen in the starting material. However, the carbon-carbon bond forms at the less-substituted carbon when the y-substituents of allyl halides are large enough (e.g., trimethylsilyl or tert-butyl) as shown by Chan et al.139 (Scheme 8.10). The following conclusions can be drawn ... 

The direct addition of simple alkyl groups onto aldehydes is the most challenging in water. Mitzel reported the indium-mediated alkylation of carbonyl compounds with a-sulfur stabilized systems.224 Recently, Li and co-workers reported an efficient addition of simple alkyl halides to aldehydes mediated by Zn/Cul with a catalytic amount of InCl in water (Eq. 8.89).225... 

Allylation of acyloyl-imidazoles and pyrazoles61 with allyl halide mediated by indium in aqueous media provides a facile regioselective synthesis of P, y-unsaturated ketones (Scheme 11.1), which has been applied to the synthesis of the monoterpene artemesia ketone. The same product can be obtained by indium-mediated allylation of acyl cyanide (Eq. 11.35).62 Samarium, gallium, and bismuth can be used as a mediator for the allylation of nitrones and hydrazones to give homoallylic hydroxylamine and hydrazides in aqueous media in the presence of Bu4NBr (Scheme 11.2).63 The reaction with gallium and bismuth can be increased dramatically under microwave activation. 

Reaction with Propargyl Halides. The indium-mediated coupling of propargyl bromide with a variety of imines and imine oxides afforded homo-propargylamine derivatives in aqueous media under mild conditions.78 Propargylation of glyoxylic oxime ether in the presence of a catalytic amount of palladium(O) complex and indium(I) iodide in aqueous media was also studied (Eq.11.47).79... 

Clerici and Porta reported that phenyl, acetyl and methyl radicals add to the Ca atom of the iminium ion, PhN+Me=CHMe, formed in situ by the titanium-catalyzed condensation of /V-methylanilinc with acetaldehyde to give PhNMeCHMePh, PhNMeCHMeAc, and PhNMeCHMe2 in 80% overall yield.83 Recently, Miyabe and co-workers studied the addition of various alkyl radicals to imine derivatives. Alkyl radicals generated from alkyl iodide and triethylborane were added to imine derivatives such as oxime ethers, hydrazones, and nitrones in an aqueous medium.84 The reaction also proceeds on solid support.85 A-sulfonylimines are also effective under such reaction conditions.86 Indium is also effective as the mediator (Eq. 11.49).87 A tandem radical addition-cyclization reaction of oxime ether and hydrazone was also developed (Eq. 11.50).88 Li and co-workers reported the synthesis of a-amino acid derivatives and amines via the addition of simple alkyl halides to imines and enamides mediated by zinc in water (Eq. 11.51).89 The zinc-mediated radical reaction of the hydrazone bearing a chiral camphorsultam provided the corresponding alkylated products with good diastereoselectivities that can be converted into enantiomerically pure a-amino acids (Eq. 11.52).90... 

Preparative hazard See Mercury(II) bromide Indium See other METAL HALIDES... 

Scheme 1. Reactions of indium halides with l,3-diisopropyl-4,5-dimethylimidazol-2-yhdene.

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