3.3.2. *N*-Benzyl-1-{(1*S*,2*R*,4*R*)-2-[(*tert*-butoxycarbonyl)amino]-7,7-dimethylbicyclo[2.2.1] heptan-1-yl}-*N*,*N*-dimethylmethanaminium Bromide (**6a**)

Following *GP2*. Prepared from compound **4a** (2.53 mmol, 748 mg) and benzyl bromide (3.795 mmol, 453 μL), K2CO3 (2.78 mmol, 385 mg), DMF (13 mL), 25 ◦C, 24 h. Isolation by column chromatography (Silica gel 60, EtOAc/MeOH = 4:1). Yield: 904 mg (1.93 mmol, 76%) of colorless oil. [α] r.t.D <sup>=</sup> −4.3 (0.26, MeOH). EI-HRMS: *<sup>m</sup>*/*<sup>z</sup>* = 387.3000 (M)+; C24H39N2O2 <sup>+</sup> requires: *m*/*z* = 387.3006 (M)+; νmax 3341, 2965, 2885, 2156, 1698, 1606, 1508, 1475, 1456, 1365, 1278, 1247, 1168, 1060, 1019, 953, 860, 782, 732, 706 cm−1. 1H-NMR (500 MHz, CDCl3): δ 0.92 (dd, *J* = 13.4, 3.5, 1H), 0.97 (s, 3H), 1.03 (s, 3H), 1.35 (t, *J* = 4.8, 1H), 1.39 (s, 9H), 1.62 (t, *J* = 4.5, 1H), 1.88–1.99 (m, 2H), 2.29 (br t, *J* = 12.9, 1H), 2.46–2.56 (m, 1H), 3.19 (s, 3H), 3.27 (s, 3H), 3.43 (br d, *J* = 14.3, 1H), 4.16–4.26 (m, 2H), 4.92 (d, *J* = 10.9, 1H), 4.97 (d, *J* = 12.4, 1H), 5.21 (d, *J* = 12.4, 1H), 7.37–7.46 (m, 3H), 7.63 (d, *J* = 6.9, 2H). 13C-NMR (126 MHz, CDCl3): δ 19.60, 20.95, 27.47, 28.40, 28.91, 40.49, 43.82, 50.54, 51.73, 53.85, 54.30, 69.39, 70.63, 80.94, 127.79, 129.12, 130.72, 133.57, 156.18.

3.3.3. 1-Benzyl-1-({(1*S*,2*S*,4*R*)-2-[(*tert*-butoxycarbonyl)amino]-7,7-dimethylbicyclo[2.2.1] heptan-1-yl}methyl)pyrrolidin-1-ium Bromide (**5b**)

Following *GP2*. Prepared from compound **3b** (2.48 mmol, 828 mg) and benzyl bromide (2.73 mmol, 324 μL), K2CO3 (2.73 mmol, 377 mg), DMF (13 mL), 25 ◦C, 24 h. Isolation by column chromatography (Silica gel 60, EtOAc/MeOH = 4:1). Yield: 469 mg (1.45 mmol, 59%) of brownish semisolid. [α] r.t.D = +17.7 (0.12, MeOH). EI-HRMS: *m*/*z* = 413.3161 (M)+; C26H41N2O2 <sup>+</sup> requires: *m*/*z* = 413.3162 (M)+; νmax 3323, 3270, 2965, 2923, 1708, 1639, 1531, 1452, 1388, 1363, 1307, 1247, 1159, 1121, 1066, 1028, 1002, 923, 901, 855, 839, 780, 710 cm−1. 1H-NMR (500 MHz, CDCl3): δ 0.92 (s, 3H), 0.91–0.96 (m, 1H), 0.96 (s, 3H), 1.32–1.35 (br t, 1H), 1.37 (s, 9H), 1.55 (t, *J* = 4.5, 1H), 1.62–1.73 (m, 1H), 1.74–1.86 (m, 2H), 1.88–2.04 (m, 2H), 2.04–2.13 (m, 1H), 2.17–2.27 (m, 1H), 2.39–2.48 (m, 1H), 3.39 (d, *J* = 14.0, 1H), 3.41–3.50 (m, 1H), 3.58–3.74 (m, 2H), 3.96 (ddd, *J* = 12.3, 8.1, 6.3, 1H), 4.13 (d, *J* = 14.0, 1H), 4.24 (tt, *J* = 10.8, 3.1, 1H), 4.59 (d, *J* = 12.6, 1H), 5.22 (br s, 1H), 5.26 (d, *J* = 10.8, 1H), 7.28–7.39 (m, 3H), 7.57 (d, *J* = 7.0, 2H). 13C-NMR (126 MHz, CDCl3): δ 19.33, 20.70, 21.60, 22.07, 27.88, 28.29, 28.81, 39.70, 43.63, 51.48, 53.44, 53.74, 59.55, 62.11, 63.58, 67.05, 80.48, 128.21, 128.99, 130.40, 133.30, 156.03.
