Herein, we disclose the Rh III -catalyzed and MeOH-assisted directC ÀHf unctionalization of simple N-alkoxybenzamides with N-cyano-N-phenyl-p-toluenesulfonamide (NCTS) in ao ne-pot cascade synthesis of 3-iminoisoindolinones with excellent substrate/functional group tolerance. Experimental studies revealt hat the versatile reaction comprises ar egioselective CÀHc yanation and subsequent intramolecularc yclization along with N-alkoxyl transfer.F urthermore, the synthetic application of the obtained products to rapidly build other important structural motifs, such as lactams and phthalazinones, has also been demonstrated in subsequentderivatizationr eactions.3-Iminoisoindolinones, structurally belonging to the N-heterocycle family,are ak ey component in numerous natural and unnatural products that display highly attractive biological and medicinal properties.[1] Moreover,t hey can serve as useful synthetic intermediates for the rapid construction of other biologically important buildingb locks.[2] Therefore, the development of efficient methods towardst heir synthesis has attracted considerable interest.In recent years, transition-metal-catalyzed CÀHf unctionalization has evolvedi nto an important and powerful tool for the step-and atom-economical construction of diversec omplex molecules with the assistance of ap roper directing group (DG), of which N-OR groups occupy ap articularly prominent position. Since it was introduced by the Fagnou group, [3] and to date, al arge number of important mono-N-heterocycles have been efficiently constructed by using aN -OR group as both DG and nitrogen atom source through transition-metalcatalyzed CÀHa ctivation/cyclization with various coupling partners. [4][5] However,t ot he besto fo ur knowledge,s of ar only aPd-catalyzed protocolf or direct synthesis of di-N-heterocycle 3-iminoisoindolinones hasb een reported by the Yu group.[6] Clearly,m ore efforts are neededt oe xplore and develop new transition-metal-catalyzed CÀHa ctivation reactions for building this privileged structural motif.Inspired by these studies and with our continued interest in Rh III -catalyzedc yclization towards N-heterocycles synthesis, [7] we herein report an ew and mild Rh III -catalyzed and MeOH-assisted direct CÀHf unctionalization of simple N-alkoxybenzamides by using N-cyano-N-phenyl-p-toluenesulfonamide (NCTS) as an environmentally friendly and highly efficient coupling partner [8] for the one-pot synthesis of 3-iminoisoindolinones with excellent regioselectivity and substrate/functional group tolerance. Notably,t he versatile reaction comprises ar egioselectiveC ÀHc yanation and subsequent intramolecular cyclization along with N-alkoxyl transfer (Scheme 1).We commencedo ur study with the reaction of N-methoxybenzamide (1a)a nd NCTS (2)i ns everal well-known examples of Rh III catalysis for reactiond evelopment (see the Supporting Information). To our delight, 3-iminoisoindolinone 3a was obtained in 62 %i solated yield by employing [Cp*Rh(OAc) 2 ] (Cp* = pentamethylcyclopentadienyl) as ...