destabilization from the lone pair interaction (Fig. ). In addition, in presence of multiple C-H bonds with similar pKa values, all positions can be deprotonated using an organolithium base. Further, several functional groups are sensitive to harsh bases and cannot withstand these conditions. The group of Glorius 42 solved this problem by using an anion stabilizing chromium catalyst (Fig. ). Unfortunately, the reactive carbanion equivalent cannot be generated directly from the C-H bond, yet requires a silicon pre-functionalization and is limited to primary alkyl nucleophiles due to chromium. A direct, site-selective carbanion generation from α-amine C-H bonds remains thus far elusive. The preparation of deuterated organic compounds is fundamentally important in drug discovery research, as deuterated drugs can change the metabolism and improve the pharmacokinetics and toxicological properties. 43 An instance is deutetrabenazine, used for the treatment of Huntington's disease. The incorporation of deuterium within the methoxy groups resulted in improved metabolic properties and fewer adverse effects compared to the non-deuterated analogue. 44 A catalytic method for the direct conversion of C-H bonds into C-D bonds with a high degree of selectivity is thus of high interest in the area of drug discovery research. Accordingly, significant advances have been made in the deuteration/tritiation of organic compounds via metal-and photocatalysis. 45-53 A notable example is the deuteration and tritiation of aromatic C(sp 2 )-H bond using a homogeneous iron catalyst, reported by the Chirik group. 48 This method shows an orthogonal selectivity to the traditional ortho-directing Crabtree iridium catalyst. There are only a few reports on the photocatalytic deuteration of C(sp 3 )-H bonds. 50,51 In 2017, the MacMillan group 54 published the first photocatalytic approach for the deuteration/tritiation of α-amino C-H bonds. While this method features impressive isotope incorporation, it is not designed to do so in a regioselective manner (Fig. ). Labelled amino acids are essential for biological in vivo and in vitro studies. The installation of deuterium in the α-position of amino acids can reduce the rate of epimerization and enhance the efficacy for elucidating biosynthetic pathways. 54,55 Although these factors are of crucial interest for scientists in research and development, the preparation of deuterated amino acids or peptides with one-pot synthesis remains an elusive, yet an urgent task. 51,56 In this regard, we herein describe a practically simple protocol for the site-selective generation of carbanions from α-amino C(sp 3 )-H bonds via a reductive radical-polar crossover, without a HAT catalyst. This method was successfully implemented in a site-specific deuteration, tritiation, and 1,2-amino alcohols synthesis (Fig. ). To the best of our knowledge, this is the first example of a photocatalytic, regioselective generation of an α-amino carbanion from a C(sp 3 )-H bond.