Transition metal catalyzed selective B(3)-H or B(4)-H amination of o-carboranes via dehydrogenative BH/NH cross-coupling


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A unique approach to vertex-selective catalytic B-H amination at either the B(3)- or B(4)-position in o-carboranes has been developed. Using different transition metal catalysts, dehydrogenative BH/NH cross-coupling of o-carboranes and free amines has been achieved, leading to a wide variety of cage B(3)- or B(4)-aminated o-carboranes in moderate to high yields with excellent regioselectivity, where carboranyl carboxylic acids and amines can serve as competent coupling partners without any pre-functionalization. The isolation and structural identification of a key intermediate provide an insight into the reaction mechanism in the catalytic B(4)-H amination.
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Key words
Transition Metal Complexes,Homogeneous Catalysis,Metal-Free Hydrogen Activation
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