Taming Inert B–H Bond with Low Energy Light: A Near-Infrared Light-Induced Approach to Facile Carborane Cluster-Amino Acid Coupling

The selective functionalization of inert B–H bonds in carborane clusters has been a formidable challenge. Recent advances have witnessed such reactions through photoredox methods utilizing ultraviolet or visible light irradiation. However, high-energy light sources often suffer from poor energy efficiency, a limited substrate scope, undesired side reactions, and low scalability. Here, we present the first successful B–H bond functionalization under low-energy near-infrared (NIR) light using a carborane-based electron donor–acceptor complex. Both photophysical investigations and theoretical modeling reveal a facile single-electron transfer from the carborane cage to the electron-deficient photocatalyst, generating a carborane cage radical under NIR light irradiation. The follow-up radical pathway enables the direct coupling of carboranes with amino acids or oligopeptides, yielding a diverse array of carborane-functionalized amino acids or oligopeptides. Beyond expanding the known chemical space of boron cluster derivatives, we further demonstrate that carborane-based amino acids with imaging and targeting capabilities could serve as promising multifunctional boron carriers for boron neutron capture therapy. Thus, the selective B–H bond functionalization of the carboranes via NIR light not only provides a straightforward and practical strategy in boron cluster synthetic chemistry but also lays the foundation for the development of next-generation boron-containing biomolecules and advanced functional materials.