Copper‐Catalyzed Electrophilic Amination of Alkoxyarylsilanes

Abstract

We report a copper‐catalyzed amination reaction between simple alkoxyarylsilanes and N‐benzoyloxyamines. Silver fluoride serves as a stoichiometric base as well as an indispensable activator that allows the catalytic process to proceed. Multiply alkoxylated arylsilanes, such as trialkoxyarylsilanes and dialkoxyarylsilanes were transformed into the corresponding tertiary anilines under mild reaction conditions.

AgF‐Mediated Electrophilic Amination of Alkoxyarylsilanes with Azodicarboxylates

“…[6] In all these cases, stoichiometric or catalytic amount of TBAF was added as a fluoride source to activate aryl siloxanes in the form of silicate intermediate. Recently, we reported a copper-catalyzed electrophilic amination of alkoxyarylsilanes with N-benzoyloxyamines (Scheme 1b), [7] where AgF was confirmed as an exceptional reagent to act as a selective stoichiometric activator. This result suggested in situ formation of an arylcopper intermediate.…”

Site-Selective Nitration of Aryl Germanes at Room Temperature

“…We initially set out to investigate electrophilic nitration conditions and explored conditions known to form nitronium ions (NO 2 + ) in situ, involving N -nitrosaccharin in HFIP . While we observed highly efficient and mild nitration of para - t -Bu phenylgermane to 1 in a 95% yield at room temperature, our further investigations revealed that extensions to intramolecular competitions of aryl germanes containing also SiMe 3 and Bpin was not feasible under these conditions due to the incompatibility of these functionalities with the employed reaction conditions. , …”