Scheme 1: Unactivated C(sp )-H bonds borylation Hydrogen atom transfer (HAT) is a general strategy in organic synthesis, and it represents an attractive approach toward remote C-H functionalization. The earliest example of remote C-H functionalization by means of HAT was Hofmann-Löffler-Freytag (HLF) reaction (Scheme 2a), the key step is the 1,5-hydrogen atom abstraction via nitrogen-centered radical, where the bond-dissociation energy (BDE) of N-H bond is higher than the C-H bond. In past decades, the nitrogen-centered radical-based HLF type reaction has shown its advances in regioselective functionalization of inert C-H bonds, by trapping the carbon-centered radicals towards the formations of C-C, C-O, C-N, and C-X (X=halogen) bonds. Particularly, amidyl radical is widely explored nitrogen-centered radical in above mentioned processes. In 2016, Knowles and Rovis 46 independently developed oxidative photocatalytic generation of amidyl radicals by direct N-H bond cleavage, after 1,5-HAT process, followed by the Michael addition of the translocated carbon-centered radical, affording the remote functionalized amides (Scheme 2b). Another way to generate amidyl radical is using activated precursors, for example, single-electron photoreduction of N -acyloxy(halo)phthalimides, N -aminopyridinium salts, and hydroxylamides give the corresponding amidyl radicals upon heterolytic cleavage of the respective leaving groups (Scheme 2c). Despite these advances, trapping the carbon-centered radical with diboron compounds to build C-B bonds, is still challenging and remains unexplored.