A. Stephen K. Hashmi

An efficient, highly selective and divergent synthetic method to construct 2‐substituted indoles and aryl‐annulated carbazoles via the intermolecular generation of α‐imino gold carbenes from terminal alkynes or diynes in combination with sulfilimines is disclosed. Importantly, the tandem reaction is proposed to proceed through an intermolecular gold carbene generation/C−H annulation followed by the activation of a second alkyne leading to 6‐ endo ‐ dig cyclization, which is significantly different from previous dual activation or 1,6‐carbene shift approaches for diyne systems. In the case of ortho ‐alkynylaniline as starting material, an unexpected regioselective formation of the indole moiety via the intermolecular path, instead of intramolecular hydroamination was discovered. This reactivity paved the way for a one‐pot synthesis of the 11 H ‐indolo [3,2‐c] quinoline scaffold by exploiting the formed amino indole for a subsequent Pictet–Spengler reaction with aldehydes. The photophysical properties of the carbazoles indicated good violet‐blue emission with quantum yields up to 40 %.