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The palladium-catalyzed Buchwald-Hartwig amination of B-iodocarborane by various azoles and amines is described for the first time. The reactions of 2-iodo-p-carborane with indole, imidazole, benzimidazole, or carbazole in the system Pd(dba) 2 -BINAP-Bu t ONa in dioxane at 100 °C gave 2-pcarboranyl derivatives of these azoles in high yields together with 2-hydroxy-p-carborane as a side product. The reactions of 2-iodo-p-carborane with aromatic amines in the same system gave the amination products in 60-70% yields and also were accompanied by the formation of hydroxy derivatives (up to 30% yields). In a special investigation it was shown that the base Bu t ONa was responsible for its formation. The principle possibility of the amination of 2-iodo-p-carborane by morpholine (with 30% yield) as an example of aliphatic amination was shown. The structures of N- (1,12-dicarba-closo-dodecaboran-2-yl) 4), and 2-hydroxy-1,12-dicarba-closo-dodecaborane (5) have been established by X-ray diffraction studies.

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The palladium-catalyzed amidation of B-iodocarboranes by various amides is described for the first time. The reactions of 2-iodo-1,12-dicarba-closo-dodecaborane (2-iodo-p-carborane) with acetamide, 2-pyrrolidinone, caprolactam, p-methylbenzamide, and 2-phenylacetamide using the system Pd(dba)2/BINAP/NaH (dba = dibenzylideneacetone; BINAP = rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) in dioxane at 100 °C gave 2-p-carboranyl derivatives of these amides in good to high yields. Similar reactions of 9-iodo-1,7-dicarba-closo-dodecaborane (9-iodo-m-carborane) with corresponding amides afforded 9-m-carboranyl derivatives in good to high yields. The structures of N-(1,12-dicarba-closo-dodecaboran-2-yl)pyrrolidin-2-one (5), N-(1,7-dicarba-closo-dodecaboran-9-yl)acetamide (6), and N-(1,7-dicarba-closo-dodecaboran-9-yl)-2-phenylacetamide (7) have been established by X-ray diffraction studies.