*3.6. Trifluoroacetate Anion Exchange—General Procedure 5 (GP5)*

The column was packed with NaI (5 g) and conditioned with ethyl acetate. The trifluoroacetate phase-transfer catalyst was dissolved in ethyl acetate and applied to the NaI column. The fractions containing the product were combined and the volatiles were evaporated in vacuo. Based on the 19F NMR spectra (presence of a signal for fluorine from trifluoroacetate anion), the procedure was repeated as necessary.

3.6.1. *N*-Benzyl-1-((1*R*,2*R*,4*R*)-2-{3-[3,5-bis(trifluoromethyl)phenyl]thioureido}-7,7 dimethylbicyclo[2.2.1]heptan-1-yl)-*N*,*N*-dimethylmethanaminium 2,2,2-Trifluoroacetate (**I**)

Following *GP4*. Prepared from compound **8a** (0.585 mmol, 300 mg) and 3,5-bis (trifluoromethyl)phenyl isothiocyanate (1.05 mmol, 192 μL), CH2Cl2 (4 mL), 25 ◦C, 16 h. Isolation by evaporation followed by column chromatography (Silica gel 60, EtOAc/MeOH = 4:1). Yield: 316 mg (0.47 mmol, 80%) of yellowish solid, mp = 87.5–89.0 ◦C. [α] r.t.D = +6.8 (0.13, MeOH). EI-HRMS: *m*/*z* = 558.2374 (M)+; C28H34F6N3S+ requires: *m*/*z* = 558.2372 (M)+; νmax 3260, 2962, 2885, 2091, 1679, 1622, 1523, 1472, 1382, 1333, 1274, 1218, 1171, 1125, 999, 970, 883, 848, 828, 780, 760, 727, 700, 680 cm−1. 1H-NMR (500 MHz, CDCl3): δ 0.89 (s, 3H); 1.18 (s, 3H); 1.36–1.45 (m, 1H); 1.66–1.74 (m, 1H); 1.81–1.94 (m, 4H); 2.22 (dd, *J* = 8.6, 13.4, 1H); 3.00 (s, 3H); 3.08 (s, 3H); 3.29 (d, *J* = 14.5, 1H); 4.65 (d, *J* = 12.6, 1H); 4.74–4.80 (m, 1H); 4.84–4.93 (m, 2H); 7.40–7.54 (m, 6H); 8.36 (s, 2H); 8.79 (d, *J* = 7.9, 1H); 10.97 (s, 1H). 13C NMR (126 MHz, CDCl3): δ 20.76, 20.93, 27.84, 34.28, 41.11, 43.92, 50.38, 50.44, 51.25, 53.08, 58.99, 66.90, 71.59, 113.57, 116.74–117.00 (m), 117.08 (q, *J* = 294.0), 122.13 (d, *J* = 4.0), 123.41 (q, *J* = 272.6), 124.49, 126.58, 129.53, 131.34 (q, *J* = 33.2), 131.37, 133.09, 141.70, 162.07 (q, *J* = 34.3), 180.02.

3.6.2. *N*-Benzyl-1-((1*R*,2*R*,4*R*)-2-{3-[3,5-bis(trifluoromethyl)phenyl]thioureido}-7,7 dimethylbicyclo[2.2.1]heptan-1-yl)-*N*,*N*-dimethylmethanaminium Iodide (**II**)

Following *GP5*. Prepared from catalyst **I** (0.21 mmol, 140 mg), dissolved in ethyl acetate (4 mL) and filtered through a pad of NaI. Volatile components were evaporated in vacuo. Yield: 140 mg (0.20 mmol, 96%) of colorless solid, mp = 61.4–62.9 ◦C. [α] r.t.D = +5 (0.19, MeOH). EI-HRMS: *m*/*z* = 558.2365 (M)+; C28H34F6N3S+ requires: *m*/*z* = 558.2372 (M)+; νmax 3305, 2964, 1674, 1536, 1473, 1384, 1336, 1275, 1172, 1123, 1000, 971, 884, 846, 801, 780, 759, 725, 701, 679 cm−1. 1H-NMR (500 MHz, CDCl3): δ 0.96 (s, 3H); 1.28 (s, 3H); 1.39–1.46 (m, 1H); 1.64–1.73 (m, 1H); 1.81–2.01 (m, 4H); 2.23 (dd, *J* = 8.8, 13.4, 1H); 3.08 (s, 3H); 3.14 (s, 3H); 3.51 (d, *J* = 14.3, 1H); 4.81–4.89 (m, 1H); 4.96 (d, *J* = 12.5, 1H); 5.07 (d, *J* = 13.9, 1H); 5.17 (d, *J* = 12.7, 1H); 7.38–7.45 (m, 2H); 7.46–7.51 (m, 1H); 7.54 (s, 1H); 7.55–7.60 (m, 2H); 8.08 (d, *J* = 8.1, 1H); 8.43 (s, 2H); 10.52 (s, 1H). 13C-NMR (126 MHz, CDCl3): δ 21.37, 21.94, 27.90, 34.23, 41.04, 43.83, 50.02, 50.70, 51.55, 53.44, 59.26, 66.70, 70.85, 117.35, 122.27, 123.36 (q, *J* = 272.7), 126.56, 129.49, 131.36, 131.36 (q, *J* = 33.3), 133.31, 141.23, 179.91.

3.6.3. 1-Benzyl-1-[((1*S*,2*S*,4*R*)-2-{3-[3,5-bis(trifluoromethyl)phenyl]thioureido}-7,7 dimethylbicyclo[2.2.1]heptan-1-yl)methyl]yrrolidine-1-ium Iodide (**III**)

Following *GP4*. Prepared from compound **7b** (0.34 mmol, 150 mg) and 3,5-bis (trifluoromethyl)phenyl isothiocyanate (0.68 mmol, 124 μL), CH2Cl2 (3 mL), 25 ◦C, 16 h. Isolation by column chromatography (Silica gel 60, EtOAc/MeOH = 10:1). Yield: 99 mg (0.14 mmol, 41%) of brownish semisolid. [α] r.t.D = +20 (0.047, MeOH). EI-HRMS: *m*/*z* = 584.2519 (M)+; C30H36F6N3S+ requires: *m*/*z* = 584.2529 (M)+; νmax 3194, 3126, 2968, 2149, 1625, 1589, 1542, 1492, 1472, 1381, 1324, 1271, 1249, 1222, 1166, 1136, 1108, 1094, 1061, 1025, 999, 967, 909, 885, 847, 756, 721, 701, 679, 612 cm<sup>−</sup>1. 1H-NMR (500 MHz, CDCl3): δ 1.03 (s, 3H); 1.06 (s, 3H); 1.15 (dd, *J* = 13.4, 3.9, 1H); 1.51–1.93 (m, 5H); 1.98–2.06 (m, 1H); 2.16–2.31 (m, 2H), 2.61–2.70 (m, 1H); 2.99–3.07 (m, 1H); 3.41–3.51 (m, 2H), 3.67–3.83 (m, 3H); 3.83–3.93 (m, 1H); 4.63 (d, *J* = 12.9, 1H); 4.96 (d, *J* = 12.8, 1H); 5.34–5.45 (m, 1H); 7.39–7.45 (m, 2H); 7.47–7.52 (m, 1H); 7.54–7.58 (m, 2H); 7.60 (s, 1H); 8.34–8.43 (m, 3H); 10.67 (s, 1H). 13C-NMR (126 MHz, CDCl3): δ 19.98, 20.65, 21.49, 21.93, 28.65, 29.57, 38.39, 43.68, 51.83, 54.54, 57.00, 60.89,

61.91, 64.34, 67.34, 117.85–118.26 (m), 123.08–123.29 (m), 123.38 (q, *J* = 209.2), 127.38, 129.67, 131.28, 131.57 (q, *J* = 33.4), 133.39, 140.92, 182.20.
