The introduction of the tryptamine derivative 4 with the pyrraline structure to 16 is the last task necessary to complete the total synthesis of 1. Because of the possible instability of the pyrraline scaffold, we planned to introduce the pyrraline moiety step by step after the introduction of protected tryptamine 19 to 18. The bioinspired activation of the tertiary amine moiety on 16 was inspired by the pioneering work of Han et al. In prior studies, it was demonstrated that the activation of tertiary amine moiety followed by C-N bond cleavage could take place using (bromodifluoromethyl)trimethylsilane. When the condition using (bromodifluoromethyl)trimethylsilane was applied to 16, 17 was successfully detected in the reaction mixture by LC-MS. It is also worth noting that the BF4 salt 17 was a stable solid and could be easily isolated by Celite ® filtration followed by concentration. This stable BF4 salt 17 is a useful intermediate that could be used for the synthesis of other related natural products. The reaction mixture of 17 was then acidified with HCl/MeOH to cleave the C-N bond and protected tryptamine 19 was added to react with intermediate 18 to give 20. The resulting 20 was successfully subjected to N-methylation by reductive amination to give 21 in 17% (5 steps). Finally, 21 was deprotected with Zn to afford a primary amine and then reacted with pyranone derivative 22 2 in AcOH at 50ºC to complete the total synthesis of 1.06 g of pyrrovobasine (1).