Gold-Catalyzed Multiple Cascade Reaction of 2-Alkynylphenylazides with Propargyl Alcohols

An unprecedented gold‐catalyzed multiple cascade reaction between 2‐alkynyl arylazides and alkynols has been developed, allowing for the step‐economical synthesis of pyrroloindolone derivatives with a wide range of structural diversity. In this reaction, the gold complex participates in triple catalysis in tandem fashion. Moreover, the efficient chirality transfer from optically pure alkynol substrates enables facile access to chiral pyrroloindolone derivatives with two stereogenic centers, including a quaternary one, with excellent levels of optical purity. Golden cascades: A gold‐catalyzed multiple cascade reaction between 2‐alkynyl arylazides and alkynols allows for step‐economical synthesis of structurally diverse pyrroloindolone derivatives by tandem catalysis. The efficient chirality transfer from optically pure alkynol substrates enables access to chiral pyrroloindolone derivatives with two stereogenic centers with excellent levels of optical purity. DCE=1,2‐dichloroethane.