Recent advances in the oxidative activation of the C2-C3 π bond of indoles and its applications

The oxidative C2-C3 π bond activation strategy is the most efficient tool to synthesize oxygen-containing indoline, which frequently appears in natural products with various biological activities as structural units. Recently, the oxidation-induced cascade strategy through oxygenation activation of the indolic C2-C3 π bond of indoles has received much attention for its use in efficiently establishing complex indoline with oxygen-containing molecular architectures, and holds tremendous potential in the total synthesis of indole alkaloids. It can be carried out using potential activated indole radical cations or imine cation intermediates produced via oxidative C2-C3 π bond activation of indole with various nucleophiles or ring-forming reagents by employing simple and non-decorated indoles as starting substrates. Herein, we have reviewed recent advances in the oxidation-induced cascade strategies connecting intra-cyclization or inter-annulation reactions, nucleophilic or radical additions and rearrangement via the oxidative C2-C3 π bond activation of indoles over the past two decades, providing diverse oxygen-containing indolines such as indoxyls, indoline oxygen-heterocycles and indolones. The features and mechanisms of different types of oxidation-induced cascade reactions have been summarized and represented, and examples have been given of their asymmetric reactions and applications in the total synthesis of indole alkaloids.