Wolff Rearrangement of α-Diazoketones Using in Situ Generated Silver Nanoclusters as Electron Mediators

We report Wolff rearrangement of α-diazoketones by in situ generated silver nanoclusters (Ag n , 2−4 nm) from silver(I) oxide (Ag2O) involving a nonclassical electron-transfer process. Our results show that Ag n +/Ag n 0 redox couple allows the initial removal of an electron from α-diazoketone and its back-donation after chemical reaction(s). Controlled potential coulometry (CPC) of various α-diazoketones results in the realization of Wolff-rearranged carboxylic acids in excellent yields.