With the optimized conditions in hand, the scope of UAAs was explored performing the reactions under air and at room temperature, using technical-grade solvents and a commercially available potentiostat (Scheme 2). (+)Mg/(-)RCV electrodes were chosen since slightly more performing than (+)Al/(-)Nifoam, although these still represent a valid option for economical reasons. Moreover, aryl bromides were employed as coupling partners since their greater availability (relative to aryl iodides) would allow a wider exploration of the chemical space. First, other protective groups on the starting aspartic acid were evaluated. To our delight, Boc and Cbz could both be tolerated under the reaction conditions, thus providing isolated UAA 3 and 4 in 57% and 36%, respectively. Despite the higher yield obtained with the Boc group, the exploration of the scope was continued using Fmoc-or Cbz-protected starting materials since this would give access to orthogonally protected UAAs. Secondly, electron-poor (hetero)aromatics other than benzaldehyde were also amenable to this chemistry, including pharmaceutically relevant diazines (products 5-9). Notably, the stereocentre remains intact during this decarboxylative arylation as demonstrated by the chiral UPLC of compound 7 (see supporting information). This is quite relevant since alternative approaches starting from dehydroalanine would furnish a racemic product. Moving toward electron-rich benzenes and 5-membered heterocycles, a slightly lower reactivity was observed, in agreement with the reduced ability of these aromatics to engage in decarboxylative arylations. Yet, a wide scope of heterocycles could be obtained in one-pot using the methodology described. For instance, thiophene-containing UAAs 11 and 12, potentially useful as fluorescent chemosensors, were obtained up to 30%. Thiazole, another ubiquitous 5-membered ring in medicinal chemistry, could be embedded too, as reported for UAAs 13-16. Interestingly, the relative position of the nitrogen atom within the structure can dramatically impact the outcome, as observed comparing regioisomeric UAAs 13 and 14. This could be attributed to the different stereoelectronic properties of the starting methylthiazole bromide which affects the catalytical cycle (e.g. irreversible coordination to nickel). Other 5-membered heterocycles incorporated for the first time in a UAA were Nmethyl-pyrazole (unsuccessful in previous studies), thiadiazole, and oxadiazole (entries 17-20), with the last three representing examples of an aromatic ring containing three heteroatoms. Isothiazole-and triazole-based coupling partners were instead unsuccessful in the decarboxylative arylation, with the mass balance given by the dimerization product of the unstable primary radical. The decarboxylative arylation could be extended also to glutamic acid, thus obtaining UAAs 21-24 bearing in the side-chain benzaldehyde (33%), 2-methylthiazole (50%), N-methyl-pyrazole (27%), and thiadiazole (27%).