Indium halides reaction with

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... 

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

A third route to allenyltin halides involves transmetallation of isolable allenyltri-butyltin compounds, as exemplified by the reaction of allenyltributyltin with Bu2SnCl2 [68]. The resulting mixture of allenyl- and propargyldibutyltin chlorides reacts with various aldehydes to afford mixtures of propargyl- and allenylcarbinols (Eqs. 9.78 and 9.79). The yields of these additions are uniformly high, but the selectivity depends on the nature of the aldehyde substituent. The transmetallation route to allenyltin and -indium halides will be discussed in more detail in a later section. 

In the Ga, In and ll group, the reaction of the trihalides with mnt2- leads66,67 to Ga(mnt)2", a mixture of In(mnt)J and In(mnt)3 and to Tl(mnt)3-, respectively. The reaction of In(mnt)2 with bipyridyl led to In(bipy)(mnt)2 , 67 Indium(I) halides react with the neutral tfd ligand to form In(tfd) halides, which were reacted further with bipyridyl under aerobic conditions to form the salt [In(tfd)2(bipy)][In(tfd)(bipy)2] containing two In111 species.68... 

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,... 

Highly regioselective radical addition of the indium hydride reagent HInCl2 to alkynes has been achieved. Various functionalities are tolerant under the reaction conditions. The reaction proceeds with complete // -stereoselectivity. Alkenylindium compounds obtained by this hydroindation can be employed for the subsequent cross-coupling reactions with aryl halides in one pot (Scheme 109).374,375... 

The Heck arylation of 2-substituted 3,4-dihydro-2//-pyrans with diazonium salts exhibits /ra 5-diastereoselectivity and leads to the 2-aryl-5,6-dihydro-27/-pyrans (Scheme 7) <03CC1656>. Tris(dihydropyranyl)indium undergoes Pd-mediated cross coupling reactions with aryl halides to give mainly 6-aryl-3,4-dihydro-2//-pyrans (Scheme 8) <030L2405>. 

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