1,2-Boryl/Hydrogen Transposition via Reversible C–H Sampling

We report a direct, photocatalytic positional exchange reaction between boronic ester groups and unactivated C–H bonds in alkylboronates. This reaction employs a reversible C–H sampling strategy combining distinct hydrogen atom abstraction (HAA) and donation (HAD) catalytic cycles, enabling exclusive 1,2-boryl translocation even in substrates with diverse distal C–H bonds. No directing groups (DGs), stoichiometric reagents, or pre-existing functional groups (FGs) are needed, and the mechanism is supported by experimental and computational evidence. By integrating on-demand boron repositioning with boron’s synthetic versatility, this method further offers valuable, strategic opportunities to enable streamlined assembly of molecular complexity.