Next, we attempted to attach the alkyne fragment 6 required for intramolecular Larock indole synthesis. In Larock indole synthesis, the TMS group is usually used as an alkyne fragment. 5 However, the TMS group was sometimes removed during the reaction in Larock indole synthesis, which leads to a decrease in regioselectivity. Therefore, we prepared an alkyne fragment 6, which has a TES group that is robust and bulkier than the TMS group. To begin with the Larock macrocyclization, 9 was easily deprotected by HCl, and the resulting amine was coupled with the prepared 6 7a by HATU to synthesize 10. The synthesis of Trp-Trp cross-links with atropisomerism has not been reported so far. Therefore, the development of scalable macrocyclization is an important issue in this study. The cyclization precursor 11, necessary for the investigation of the intramolecular Larock indole synthesis, was obtained from 10 in 43% yield (2 steps) by selective reduction of the nitro group with Fe dust and NH4Cl.