Enantioselective Dearomatization of Indoles by an Azoalkene‐Enabled (3+2) Reaction: Access to Pyrroloindolines

Abstract The enantioselective dearomatization of indoles by an organocatalytic (3+2) reaction has been established. The reaction makes use of simple indole derivatives as substrates, and employs azoalkenes reaction partners. A wide range of pyrroloindolines containing an all‐carbon quaternary stereogenic center were readily prepared in high yields and with excellent enantioselectivities.