Compound 9

Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.

To a flask charged with triflate 8 was added Pd(PPh₃)₄ (791 mg, 0.68 mmol, 0.10 equiv) and CuI (260 mg, 1.36 mmol, 0.2 equiv) in the glovebox. The flask was removed from the glovebox and propargyl alcohol (515 µL, 8.89 mmol, 1.3 equiv) was added, followed by NEt₃ (1.43 mL, 10.27 mmol, 1.5 equiv) and DMF (46 mL). The reaction mixture was sparged with N₂ for 10 min, and stirred at 60 °C for 16 h. The reaction was allowed to cool to room temperature and quenched with sat. aq. NH­₄Cl (100 mL), then diluted with H₂O (100 mL) and EtOAc (200 mL). The layers were separated, and the aqueous layer was extracted with EtOAc (3 x 150 mL). The combined organic layers were washed with brine (2 x 100 mL) and dried over Na₂SO₄. Evaporation under reduced pressure afforded the crude product, which was purified by flash chromatography (7:3 Hexanes:EtOAc) to provide propargyl alcohol 9 (1.9 g, 84% yield) as a white solid. Mp: 132–136 °C; R_f 0.20 (7:3 Hexanes:EtOAc); ¹H NMR (500 MHz, CDCl₃): δ 8.26 (s, 1H), 8.01 (d, J = 7.8, 1H), 7.70 (s, 1H), 7.49–7.55 (m, 2H), 7.28–7.31 (m, 1H), 5.63 (s, 2H), 4.61 (d, J = 5.8, 2H), 3.29 (s, 3H), 1.74 (t, J = 6.0, 1H); ¹³C NMR (500 MHz, CDCl₃): δ 141.6, 139.1, 127.4, 125.2, 123.9, 122.0, 121.1, 120.82, 120.76, 116.0, 114.3, 109.6, 91.2, 85.4, 74.3, 56.3, 51.9; IR (film): 3379, 2931, 1600, 1468, 1451, 1429, 1337, 1241, 1110, 1060, 1035, 1024 cm^–1; HRMS-APCI (m/z) [M]^•+ calcd for C₁₇H₁₄BrNO₂, 343.0202; found, 343.0190.