Migration at Boron Cage for Selective B-H Functionalization of nido-Carboranes.

Area of Science:

• Boron cluster chemistry
• Synthetic organic chemistry
• Materials science

Background:

• Molecular rearrangement is a key strategy for synthesizing complex molecules.
• Transformations of boron clusters, particularly B-H bond functionalization, are underdeveloped.
• Conventional methods struggle to access specific functionalization positions in boron clusters.

Purpose of the Study:

• To develop a novel strategy for selective B-H bond functionalization in nido-carboranes.
• To enable access to synthetically challenging positions on the boron cage.
• To expand the synthetic utility of boron clusters for diverse applications.

Main Methods:

• Development of a nucleophile-induced rearrangement strategy for B-O substituted nido-carboranes.
• Utilized diverse nucleophiles (N-heterocycles, thioethers) to orchestrate boron cage migration.
• Employed high-valent iodine reagents to facilitate the reaction pathway.

Main Results:

• Achieved selective functionalization of B-H bonds at previously inaccessible positions.
• Demonstrated synthetic utility through post-modification of drug molecules.
• Synthesized novel boron delivery agents (with 13C labeling for boron neutron capture therapy [BNCT]), carborane-based luminogens exhibiting aggregation-induced emission (AIE), and efficient reactive oxygen species (ROS) generators.

Conclusions:

• Established a new paradigm for B-H bond functionalization in boron clusters via cage migration.
• Significantly expanded the synthetic toolbox for constructing functional molecules based on boron clusters.
• The developed method offers a versatile platform for creating advanced boron-containing materials and therapeutics.