| Abstract
| - The palladium-catalyzed Buchwald−Hartwig amination of B-iodocarborane by various azoles andamines 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−ButONa in dioxane at 100 °C gave 2-p-carboranyl 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 productsin 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 ButONa was responsible for its formation. Theprinciple possibility of the amination of 2-iodo-p-carborane by morpholine (with 30% yield) as an exampleof aliphatic amination was shown. The structures of N-(1,12-dicarba-closo-dodecaboran-2-yl)carbazole(1), N-(1,12-dicarba-closo-dodecaboran-2-yl)benzimidazole (2), N-(1,12-dicarba-closo-dodecaboran-2-yl)indole (4), and 2-hydroxy-1,12-dicarba-closo-dodecaborane (5) have been established by X-raydiffraction studies.
- The first study of the amination of 2-iodo-p-carborane at the boron atom by azoles, anilines, and morpholine using the system Pd(dba)2−BINAP−ButONa in dioxane at 100 °C is described. p-Carboran-2-yl derivatives of carbazole, benzimidazole, and indole are the first compounds with a B−N bond in p-carborane characterized by X-ray structure analysis.
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