Total Synthesis of (−)‐Arborisidine

Abstract An asymmetric total synthesis of cage‐like indole alkaloid arborisidine is presented. The new synthetic strategy features a catalytic parallel kinetic resolution based on ambident nucleophilicity (C3/N) of indole to set the absolute configurations of the two quaternary chiral centers, and a 5‐ exo‐trig radical cyclization to form the bridged nitrogen‐containing five‐membered ring.