A novel visible‐light‐induced radical cascade trifluoromethylation/cyclization of N‐benzamides with CF3SO2Na has been achieved. This protocol provides an efficient strategy for the synthesis of CF3‐containing isoquinoline‐1,3‐diones under mild reaction conditions. The reaction features metal‐free, air oxidation, CF3SO2Na as CF3 source, additives free and operational simplicity. Moreover, the representative products displayed significant potencial antifungal activities in vitro.
Density functional theory calculations were performed to study the reaction mechanism of Rh(I)‐catalyzed, P(III)‐directed regioselective CH arylation of indole with anhydride through decarbonylative cross‐coupling. This mechanism involves four major steps: CH activation, oxidative addition, decarbonylation, and reductive elimination. Through this theoretic study, we find that the CH bond activation was accomplished by the hydrogen carbonate (−HCO3)‐assisted concerted metalation‐deprotonation (CMD) process, not through the oxidative addition of Rh(I)‐catalyst. Meanwhile, our calculation results indicate that the regioselectivity of CH bond arylation of indole with anhydride can be attributed to the relative stability of the CMD transition states in the CH bond activation process. Moreover, in the CH activation step, the base (−HCO3) is not coordinated with the Rh center.
The reaction mechanism of Pd 2+ -catalyzed regioselective C-H alkylation of indole with MesICH 2 CF OTf has been investigated by the density functional theory calculations. The reaction mechanism mainly contains four steps C-H activation, oxidative addition, reductive elimination and ligands substitution.From our calculations, we nd that the C-H activation step was realized by the acetate anion ( -OAc) assisted CMD process and the transition state of C-H activation process is a square planar con guration. Moreover, the calculation results suggest that the regioselectivity of C-H bond alkylation of indole with MesICH 2 CF 3 OTf can be ascribed to the different stability of the CMD transition states in C-H activation step and different acidities of C-H bonds.
The reaction mechanism of Pd2+-catalyzed regioselective C–H alkylation of indole with MesICH2CF3OTf has been investigated by the density functional theory calculations. The reaction mechanism mainly contains four steps:C-H activation, oxidative addition, reductive elimination and ligands substitution. From our calculations, we find that the C-H activation step was realized by the acetate anion (-OAc) assisted CMD process and the transition state of C-H activation process is a square planar configuration. Moreover, the calculation results suggest that the regioselectivity of C-H bond alkylation of indole with MesICH2CF3OTf can be ascribed to the different stability of the CMD transition states in C-H activation step and different acidities of C-H bonds.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.