Indium bromide hydride

Indium trichloride induces rearrangement of aryl-substituted epoxides to the respective aryl-substituted acetaldehydes via an exclusive hydride shift As phenyl group migration occurs more readily than hydride migration, stilbene oxide is converted to diphenylacetaldehyde (Scheme 8.140) [184]. N-Tosyl aziridines react smoothly with carboxylic acids in the presence of a catalytic amount of indium triflate to afford the corresponding -aminoacetates and benzoates (Scheme 8.141) [185]. Indium trichloride and indium bromide catalyze regio- and diastereoselective azidolysis, bromolysis, and iodolysis of a, -epoxycarboxylates in water (Scheme 8.142) [186]. 

A number of indium trialkyls have been prepared, starting from the trimeihyl, and some diaryl compounds are known, such as the diphenyl bromide. The lower trialkyls are tetramers. Like aluminum, indium forms a polymeric hydride. (lnHil , from which lelrahydroindates. such as the lithium compound, LilnHj. can be derived. 

Dichloroindium hydride (Cl2InH), generated by the reaction of InCl3 with tributyltin hydride, is also successfully used for the reduction of carbonyl compounds and for the debromination of alkyl bromides.366 This reductant has features such as the chemoselective reduction of functionalized benzaldehydes, chelation-controlled reduction of benzoin methyl ether, and 1,4-reduction of chalcone. The stable carbene and tertiary phosphine adducts of indium trihydride, InH3 CN(Mes)CH=CHN(Mes) and InH3 P(c-G6H11)3, reduce ketones to alcohols (Equation (90)).367... 

Dichloroindium hydride HlnCla, prepared from indium(m) chloride and DIBAL-H, works as a radical mediator. This compound reduces aryl iodides and bromides in the presence of Et3B as a radical initiator. Reduction of iodoacetals provides cyclized products in good yields (Equation (99)).385 Only a catalytic amount of InCl3 is necessary for complete consumption of the starting compound with stoichiometric DIBAL-H as a hydride source (Equation (100)). 

Hydrogen bromide Hydrogen chloride Hydrogen fluoride Indium hydride Rubidium hydride Stibine... 

---