Route A: To a solution of 2-bromo-3-methoxybenzo [b]biphenylene (5, 230 mg, 0.76 mmol) in dry CH2Cl2 (27 mL) cooled to -78 °C, BBr3 (1.30 mL, 1M in CH2Cl2, 1.30 mmol) was added. After 1 h, the reaction mixture was warmed up to room temperature and stirring was kept for 14 h. The reaction mixture was quenched with H2O/ice and extracted with CH2Cl2 (3 x 20 mL). The combined organic layer was dried with Na2SO4, filtered and evaporated under reduced pressure. After observed the quantitative formation of phenol by TLC the crude was used in the next step without any further purification. The crude phenol, previously isolated, was dissolved in THF (5 mL), HMDS (175 mL, 0.83 mmol) was added and the reaction mixture was refluxed for 1.5 h. The solvent and excess HMDS were removed under reduced pressure. The crude residue was dissolved in dry THF (3 mL), the solution was cooled down to -100 °C and, then, n-BuLi (365 mL, 2.3 M, 0.84 mmol) was added dropwise. After warming up the reaction mixture to -80°C, it was cooled again to -100°C and Tf2O (155 mL, 0.91 mmol) was added. The reaction mixture was allowed to reach -80 °C and then quenched with NaHCO3 (aqueous saturated solution, 5 mL). After being warmed to room temperature, the phases were separated, the aqueous layer was extracted with CH2Cl2 (2 x 20 mL), and the combined organic layers dried with Na2SO4, filtered and evaporated under reduced pressure. The crude residue was purified by column chromatography on silica gel (hexane/CH2Cl2, 9:1) yielding triflate 2 as a pale yellow solid (177 mg, 55 %).