3.2.6. Compound **11**

Colorless gum (1.2 mg, 4%); UV (MeOH) λmax (log ε) 237 (3.94), 327 (2.96) nm; IR (UATR) νmax 3436, 2986, 1747, 1705, 1280, 1199, 1166, 1078, 1026, 975, 712 cm−1; 1H NMR (800 MHz, CD3OD) δ<sup>H</sup> 2.00–2.11 (4H, m, H-10, H-14), 2.12–2.21 (4H, m, H-11, H-13), 3.71 (1H, m, H-9), 3.99 (3H, s, 6-OMe), 4.03 (3H, s, 7-OMe), 7.28 (1H, s, H-5), 7.52 (1H, d, *J* = 5.7 Hz, H-4), 7.54 (1H, s, H-8), 8.19 (1H, d, *J* = 5.7 Hz, H-3); 13C NMR (200 MHz, CD3OD) δ<sup>C</sup> 29.6 (2C, d, <sup>3</sup>*J*CF = 10.3 Hz, C-10, C-14), 34.8 (2C, dd, <sup>2</sup>*J*CF = 25.5, 22.6 Hz, C-11, C-13), 40.2 (C-9), 56.46 (6-OMe), 56.54 (7-OMe), 104.2 (C-8), 106.9 (C-5), 119.9 (C-4), 123.3 (C-8a), 124.5 (dd, <sup>1</sup>*J*CF = 242.0, 239.2 Hz, C-12), 135.2 (C-4a), 140.9 (C-3), 152.0 (C-7), 154.5 (C-6), 162.3 (C-1); (+)-LRESIMS *m*/*z* (rel. int.) 308 (100) [M + H]+; (+)-HRESIMS *m*/*z* 308.1454 [M + H]<sup>+</sup> (calcd for C17H20F2NO2, 308.1457).

#### *3.3. Generation of the Papaverine Library (TFA-Addition Method): Compounds 6–8 and 10*

Papaverine hydrochloride (**1a**, 37.5 mg, 0.1 mmol) was dissolved in CH2Cl2/H2O or DMSO/H2O (2.5:1, 100 μL:40 μL) before the addition of the sulfinate reagent (85.6–198.9 mg, 0.6 mmol) and TFA (7.7 μL, 0.1 mmol) at room temperature. The mixture was cooled to 0 ◦C before TBHP (40 μL, 0.6 mmol) was slowly added, after which time, the stirred mixture slowly warmed to room temperature over 16 h. Crude reaction products was dried under N2 and pre-adsorbed to NH2-bonded silica (≈1 g) overnight before being subjected to identical NH2 semi-preparative HPLC conditions, which are described above. This method generated compound **6** using the CH2Cl2/H2O solvent system, while compounds **7**, **8**, and **10** were generated using the DMSO/H2O mixture.

#### 3.3.1. Compound **6**

Colorless gum (1.0 mg, 3%); UV (MeOH) λmax (log ε) 240 (4.15), 273 (3.36), 327 (3.08) nm; IR (UATR) νmax 3458, 2981, 1747, 1705, 1278, 1199, 1165, 1078, 1026, 975, 712 cm<sup>−</sup>1; 1H NMR (800 MHz, CD3OD) δ<sup>H</sup> 3.72 (3H, s, 12-OMe), 3.76 (3H, s, 13-OMe), 3.87 (3H, s, 7-OMe), 3.98 (3H, s, 6-OMe), 4.57 (2H, s, H-9), 6.78 (1H, dd, *J* = 8.3, 2.0 Hz, H-15), 6.83 (1H, d, *J* = 8.3 Hz, H-14), 6.84 (1H, t, *J* = 55.7 Hz, H-16), 6.93 (1H, d, *J* = 2.0 Hz, H-11), 7.37 (1H, s, H-5), 7.48 (1H, s, H-8), 7.88 (1H, s, H-4); 13C NMR (200 MHz, CD3OD) δ<sup>C</sup> 42.0 (C-9), 56.4 (12-OMe), 56.45 (13-OMe), 56.49 (7-OMe), 56.6 (6-OMe), 107.4 (C-5), 105.8 (C-8), 113.2 (C-14), 113.6 (C-11), 115.6 (t, <sup>1</sup>*J*CF = 238.0 Hz, C-16), 117.4 (t, <sup>3</sup>*J*CF = 4.8 Hz, C-4), 121.9 (C-15), 125.0 (C-8a), 133.4 (C-10), 135.0 (C-4a), 144.9 (t, <sup>2</sup>*J*CF = 24.3 Hz, C-3), 149.2 (C-13), 150.6 (C-12), 152.6 (C-7), 154.9 (C-6), 160.1 (C-1); (+)-LRESIMS *m*/*z* (rel. int.) 390 (100) [M + H]+; (+)-HRESIMS *m*/*z* 390.1506 [M + H]<sup>+</sup> (calcd for C21H22F2NO4, 390.1511).
