The synthetic approach towards cihunamide B (1) is shown in Figure . The development of a rapid and scalable synthesis of cihunamide B (1) is of paramount importance in this study. Thus, a robust synthesis strategy was employed that could withstand scalable synthesis. In particular, we planned to use inexpensive and simple building blocks, L-tryptophan derivative 2, 1-bromo-3fluoro-2-nitrobenzene 3, and L-isoleucine derivative 4, L-aspartic acid derivative 5 and alkyne fragment 6 as starting materials in a reliable reaction that proceeds under mild conditions. The unprecedented unique atrop-C-N bond was planned to be synthesized by introducing an aromatic ring through the SNAr reaction of 3 with the tryptophan derivative 2, followed by an intramolecular Larock indole synthesis of the alkyne moiety of 6. For the efficient and scalable synthesis of cihunamide B (1), this intramolecular Larock indole synthesis needs to proceed in an atroposelective manner. The atroposelectivity of the C-N bond was expected to be controlled by substrate control to achieve the desired atroposelectivity.