ABSTRACT Molecular rearrangement provides a powerful pathway to structurally unique and synthetically inaccessible molecules. To date, however, such transformations remain underdeveloped for boron clusters. Herein, we disclose a strategy for the selective functionalization of B–H bonds in nido ‐carboranes via an unprecedented migration at the boron cage. This process orchestrates a rearrangement of B–O substituted nido ‐carboranes upon reaction with diverse nucleophiles, including N‐heterocycles and thioethers, thus enabling the B–H functionalization at a position that is inaccessible through conventional methods. Its synthetic utility is demonstrated through facile post‐modification of drug molecules, synthesis of new boron delivery agents with 13 C labeling for boron neutron capture therapy (BNCT), and construction of carborane‐based luminogens that exhibit aggregation‐induced emission (AIE) and efficient reactive oxygen species (ROS) generation. Mechanistic investigations support a pathway involving nucleophile‐induced migration at the boron cage, facilitated by a high‐valent iodine reagent. This work establishes a paradigm for the B–H bond functionalization of boron clusters via migration at the boron cage, thereby expanding the synthetic toolbox for constructing functional molecules based on boron clusters.
Zhang et al. (Mon,) studied this question.