In our recent report on the total synthesis of cihunamide B, we demonstrated that Larock macrocyclization using Pd(OAc)2 and tBu3P is effective for constructing the highly strained atrop-Trp-Trp linkage. Accordingly, the cyclization precursor 22 was heated in PhMe at 110 °C and subjected to Larock macrocyclization using Pd(tBu3P)2 and DIPEA. Despite the significant strain, this Larock macrocyclization proceeded, yielding the desired cyclized product 28 with atropisomerism (Sa) and the cyclized product 25 with the opposite atropisomerism (Ra) in a 1:1 ratio with an isolated yield of 61%. Remarkably, this Larock macrocyclization was successfully carried out on a decagram scale, producing 9.9 g of highly strained Tyr-Trp linkage-bearing cyclized products 25 and 28 as a 1:1 mixture.