To overcome the drawback that only N-arylation byproducts were generated in reactions using a strong electronwithdrawing group-substituted 2-nitro fluorobenzene, corresponding 2-nitro chlorobenzenes were employed as reactants. As expected, the desired C-arylation became dominant, and only a small amount of N-arylation was observed. For example, nitro, cyano, trifluoromethyl, and ester-substituted 2-nitro chlorobenzenes gave products 3af-3aj in good-to-high yields with excellent enantioselectivities (Figure ). 8-Fluoro-5-nitroquinoline was also a suitable reaction partner with amino acid ester 1a, which gave products 3ak in 62% yield with 70% ee. Furthermore, when ethyl 2fluoro-5-nitrobenzoate was used as an arylation reagent, optically active chiral isoindolinones were produced via a tandem arylation/cyclization process (Figure ). The absolute configuration of product 3a was assigned as S by comparing its optical rotation value with the literature data (see Supplementary Information), and the stereochemistries of the other products in Figure were assigned accordingly.