The efficient o-carboryne precursor 1-Li-2-OTf-o-C₂B₁₀H₁₀ reacts with lithium amides at room temperature to give a series of N-carboranyl amines in moderate to high isolated yields. This reaction is compatible with a broad substrate scope from primary to secondary, alkyl to aryl amines. The reaction mechanism is also proposed on the basis of experimental results and DFT calculations. This represents the first general and efficient method for the synthesis of 1-NR¹R²-o-carboranes.

The efficient o-carboryne precursor 1-Li-2-OTf-o-C₂B₁₀H₁₀ reacts with lithium amides at room temperature to give a series of N-carboranyl amines in moderate to high isolated yields. This reaction is compatible with a broad substrate scope from primary to secondary, alkyl to aryl amines. The reaction mechanism is also proposed on the basis of experimental results and DFT calculations. This represents the first general and efficient method for the synthesis of 1-NR¹R²-o-carboranes.

o-Carboryne (1,2-dehydro-o-carborane) generated in situ from the precursor 1-iodo-2-lithio-o-carborane reacts with 6,6′-diarylfulvenes to give a series of carboranonorbornadienes in moderate yields with excellent regioselectivity. The resultant [4+2] cycloadducts can be further derivatized, thus leading to the formation of a variety of highly functionalized carboranes. This study shows that such Diels–Alder reaction serves as a convenient method for the preparation of a new class of multifunctionalized o-carborane derivatives that might find applications in medicine and materials science.