Total Synthesis of Calophyline A

Reported herein is the total synthesis of calophyline A, an indoline natural product possessing distinct ring connectivity which has not been synthesized previously. The synthetic route features several key transformations, including an aza‐pinacol rearrangement to construct the nitrogen‐containing bridged 3.2.2] bicycle, a Heck cyclization to assemble the fused 6/5/6/5 ring system, and a challenging late‐stage aldol reaction to generate both a neopentyl quaternary stereogenic center and an oxygen‐containing bridged 3.2.1] bicycle.