(-)-Angustureine is an important member of the tetrahydroquinoline alkaloid family. Such natural products have attracted the attention of synthetic chemists because of their potential biological activities. Starting from methyl (R)-N-Boc- indoline-2-carboxylate, the enantioselective total synthesis of (-)-angustureine was accomplished in 7 steps. The key step of our synthesis involves a rearrangement ring-expansion reaction. © 2021 Chinese Chemical Society & SIOC, CAS.