did not deliver any diamines, neither. Instead, the C-H amidation products 44 and 45, resulting from the re-aromatization after the addition of N-centered amidyl radical to indoles, were obtained in 16% and 15% yields, respectively. These results suggested that the electron withdrawing group at the indole N atom is indispensable for the dearomative diamination. We speculated that the electron withdrawing group at the indole N atom might decrease the nucleophilicity of C-centered benzyl radical, thereby improving the polar match with ambiphilic N-centered iminyl radiacal. This ultimately facilitated the reaction to proceed smoothly toward the desired dearomative diamination rather than the rearomative C-H amidation. In addition, the protocol could be smoothly extended to various benzofurans including xanthotoxin (Fig. , 46-55), as well as benzothiophenes (Fig. , 56-58). Surprisingly, conjugated arenes, such as phenanthrene and anthracene, despite with lower reactivity, were also found suitable for this transformation, forming the products in decent yields (Fig. , 59-60). Most notably, high diastereoselectivity was obtained within these diamination reactions because the stepwise addition of amidyl and iminyl radicals across carbon-carbon bonds proceeded from the opposite, sterically accessible side, producing a series of cyclic trans-diamines. Then, the applicability of this method towards alkene substrates was examined as well. As summarized in Fig. , a wide range of alkenes, ranging from styrenes, cyclic alkenes, enynes, electron-poor or rich alkenes, to even unactivated alkenes could participate in the reaction (61-98), delivering the corresponding unsymmetrical diamines in moderate to good yields and with excellent regioselectivity. It is of note that acyclic 1,2-disubstituted alkenes were also suitable for this reaction. For example, (E)-prop- Subsequently, to highlight the synthetic usefulness of this method, a 10 mmol scale reaction of H3 with S8 was performed under the standard reaction conditions, providing 3.2 gram of product 20 in 56% yield (Fig. ). Moreover, either imine or amide units on compound 20 were orthogonally deprotected under mild conditions to give the corresponding unprotected amines (99 and 100), thereby facilitating the downstream transformation. Similarly, the orthogonal deprotections of product 61 were conducted (Fig. , 101 and 102). Thus, this protocol offers a general access to diamine precursors which could be selectively converted into synthetically relevant unsymmetrical diamine products. Additionally, treatment of product 76 with HCl (6 N) at 100 o C for 12 h generated a valuable 1,2-diamino acid 103 (Fig. ). Finally, N-alkyl substituted bifunctional nitrogen-radical precursors S13 and S14 were easily prepared through Mitsunobu reaction of S8 with EtOH or CD 3 OD in excellent yields. To our delight, S13 and S14 smoothly underwent this reaction, producing the desired diamines in moderate yields (104 and 105). These results further extended the scope of bifunctional nitrogen-radical precursors, and highlighted the practicality of this method.