Organoindium reactions with

The use of an organoindium glucal in palladium catalyzed [Pd(PPh3)2] cross-coupling reactions with aryl iodides gave moderate yields (40-60%) of C-l aryl glucals.45... 

Intermolecular adducts of organoindium can be prepared in a hydrocarbon solvent by reaction with a Lewis base (equation 21), or via displacement of more labile adducts... 

Reaction with diselenides. Organoindiums derived from allyl or propargyl halides and a-halo ketones react with diselenides to afford unsaturated selenides and a-seleno ketones, respectively. 

At room temperature In[CH2(SiMe3)]3 is a colorless pyrophoric liquid. The H NMR spectrum of the compound in benzene (reference 8 7.13) consists of two lines in area ratio 9 2, with the larger methyl line at 8 -1-0.13 and the smaller methylene line at 8 -O.OS.t The IR spectrum of the neat liquid has bands at 2935 (vs), 2885 (s,sh), 1440 (w), 1400 (w), 1350 (w), 1291 (w,sh), 1244 (vs), 920 (s), 825 (vs), 757 (vs), 720 (vs), 692 (s,sh), 580 (m), and 490 (m) cm". The compound can be used to prepare [(trimethylsilyl)methyl]indium halogen compounds by appropriate stoichiometric exchange reactions with InClj, InBrj, and Ini. Properties of many of these organoindium halogen compounds have been reported. The experimental procedure is related to that described for Al(CH2SiMe3)2Br, except that solvents are used for the reactions. 

Organoindium reagents can also be used in the crosscoupling reaction with imines via copper(I) chloride catalysis. Copper-catalyzed direct amination of nitrobenzenes with O-alkylhydroxylamines is known however, more general ami-nation and amidation reactions involve activation of aryl halides with CuCl and l,10-phenanthroline(phen) or other sterically well-defined ligands. ... 

Hsieh ATT. Organoindium derivatives. 1. Reactions of some organoindium compounds with sulphur dioxide. J. Org. Chem. 1971 27(3) 293-301. 

The nucleophilic reaction of Grignard reagents with azetidin-2,3-dione 270 yielded mainly fA-3-hydroxyazetidin-2-ones 271 (Equation 76) <2006S115>. A regio- and stereoselective reaction of azetidine-2,3-dione 272 with an organoindium compound led to the formation of azetidin-2-one-tethered homoallylic alcohol 273 (Equation 77), which has been used as precursor of spirocyclic azetidin-2-ones <2004TL6429>. 

A large part of organoindium chemistry so far reported deals with reactions of allylic and propargylic indium reagents. These are summarized in Sections 9.14.3.1-9.14.3.9. Reactions of other type of organoindium compounds are overviewed in Sections 9.14.3.10-9.14.3.14. 

The organoindium reagent, prepared from indium metal and bromoacetonitrile, reacts with carbonyl compounds in the presence of chlorotrimethylsilane to give /3-hydroxy nitriles (Scheme 93),336 337 Similarly, indium-mediated coupling of bromoacetonitrile or 2-bromopropionitrile with a variety of aromatic acyl cyanides affords the corresponding aromatic a-cyanoketones in moderate to good yields under mild and neutral conditions (Equation (86)).338 Carbonyl compounds are efficiently transformed into 2,2-dichloro-3-hydroxynitriles by the action of trichloroaceto-nitrile and indium(i) bromide (Scheme 94).339 Bromocyanomethylation of carbonyl compounds is also achieved by the reaction of dibromoacetonitrile and indium(i) bromide.340... 

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