*3.2. Boc Protection of Chiral Amines—General Procedure 1 (GP1)*

To a solution of amine **1** or **2** and triethylamine (1.4 equivalents) in anhydrous CH2Cl2 was added di-*tert*-butyl dicarbonate (1.4 equivalents). The resulting reaction mixture was stirred at 25 ◦C for 24 h. Dichloromethane was evaporated in vacuo and the residue was purified by column chromatography (CC). The fractions containing product **3** or **4** were combined and the volatiles were evaporated in vacuo.

3.2.1. *tert*-Butyl {(1*S*,2*S*,4*R*)-1-[(dimethylamino)methyl]-7,7-dimethylbicyclo[2.2.1] heptan-2-yl}carbamate (**3a**)

Following *GP1*. Prepared from *endo*-amine **1a** (4.69 mmol, 920 mg) and di-*tert*-butyl dicarbonate (6.56 mmol, 1.431 g), Et3N (6.56 mmol, 915 μL), CH2Cl2 (20 mL), 25 ◦C, 24 h. Isolation by column chromatography (Silica gel 60, EtOAc/petroleum ether = 1:5). Yield: 1.39 g (4.69 mmol, 99%) of colorless oil. [α] r.t.D = +11.2 (0.15, MeOH). EI-HRMS: *m*/*z* = 297.2646 (MH)+; C17H33N2O2 <sup>+</sup> requires: *m*/*z* = 297.2536 (MH)+; νmax 3346, 2935, 2819, 2765, 1698, 1483, 1454, 1389, 1364, 1297, 1242, 1167, 1114, 1065, 1040, 1014, 946, 874, 837, 780 cm−1. 1H-NMR (500 MHz, CDCl3): δ 0.86 (s, 3H), 0.90 (s, 3H), 1.04 (dd, *J* = 13.4, 4.3, 1H), 1.21 (ddd, *J* = 12.2, 9.5, 4.4, 1H), 1.43 (s, 9H), 1.45–1.51 (m, 1H), 1.56 (t, *J* = 4.6, 1H), 1.72 (tq, *J* = 12.1, 4.1, 1H), 1.86 (br t, 1H), 2.21 (s, 6H), 2.24 (d, *J* = 13.6, 1H), 2.28–2.33 (m, 1H), 2.36 (d, *J* = 13.8, 1H), 3.75 (s, 1H), 6.00 (s, 1H). 13C-NMR (126 MHz, CDCl3): δ 19.19, 20.31, 25.40, 28.39, 28.64, 37.92, 45.07, 48.10, 48.33, 50.98, 56.25, 61.97, 78.72, 157.52.

3.2.2. *tert*-Butyl {(1*S*,2*R*,4*R*)-1-[(dimethylamino)methyl]-7,7-dimethylbicyclo[2.2.1] heptan-2-yl}carbamate (**4a**)

Following *GP1*. Prepared from *exo*-amine **2a** (0.81 mmol, 160 mg) and di-*tert*-butyl dicarbonate (1.134 mmol, 247 mg), Et3N (1.19 mmol, 166 μL), CH2Cl2 (4 mL), 25 ◦C, 24 h. Isolation by column chromatography (Silica gel 60, EtOAc/petroleum ether = 1:5). Yield: 230 mg (0.78 mmol, 95%) of colorless oil. [α] r.t.D = +25.7 (0.175, MeOH). EI-HRMS: *m*/*z* = 297.2536 (MH)+; C17H33N2O2 <sup>+</sup> requires: *m*/*z* = 297.2537 (MH)+; νmax 3344, 2935, 2819, 2765, 1698, 1484, 1453, 1389, 1364, 1297, 1243, 1167, 1113, 1065, 1040, 1004, 943, 874, 837, 780 cm−1. 1H-NMR (500 MHz, CDCl3): δ 0.87 (s, 3H), 0.99 (s, 3H), 1.09–1.17 (m, 1H), 1.34 (t, *J* = 9.4, 1H), 1.42–1.45 (m, 1H), 1.43 (s, 9H), 1.67 (d, *J* = 3.5, 2H), 1.69–1.75 (m, 1H), 1.86 (d, *J* = 8.4, 1H), 2.24 (s, 6H), 2.25 (d, *J* = 13.9, 1H), 2.40 (d, *J* = 13.9, 1H), 3.71 (br s, 1H), 5.58 (br s, 1H). 13C-NMR (126 MHz, CDCl3): δ 20.95, 27.15, 28.50, 28.67, 30.48, 33.79, 40.55, 45.67, 48.03, 50.94, 57.44, 58.86, 78.90, 155.72.

3.2.3. *tert*-Butyl [(1*S*,2*S*,4*R*)-7,7-dimethyl-1-(pyrrolidin-1-ylmethyl)bicyclo[2.2.1] heptan-2-yl}carbamate (**3b**)

Following *GP1*. Prepared from *endo*-amine **1b** (3.91 mmol, 869 mg) and di-*tert*-butyl dicarbonate (5.474 mmol, 1.194 g), Et3N (5.474 mmol, 763 μL), CH2Cl2 (20 mL), 25 ◦C, 24 h. Isolation by column chromatography (Silica gel 60, EtOAc/petroleum ether = 1:5). Yield: 1.251 g (3.88 mmol, 99%) of brownish oil. [α] r.t.D = +1.1 (0.295, MeOH). EI-HRMS: *m*/*z* = 323.2688 (MH)+; C19H35N2O2 <sup>+</sup> requires: *m*/*z* = 323.2693 (MH)+; νmax 3300, 2979, 2937, 2879, 2794, 1808, 1757, 1715, 1460, 1395, 1371, 1306, 1250, 1211, 1168, 1113, 1062, 950, 844, 775, 664 cm−1. 1H-NMR (600 MHz, CDCl3): δ 0.85 (s, 3H), 0.90 (s, 3H), 1.07 (dd, *J* = 13.4, 4.4, 1H), 1.21 (ddd, *J* = 12.8, 9.5, 4.5, 1H), 1.4–1.45 (m, 1H), 1.41 (s, 9H), 1.56 (t, *J* = 4.6, 1H), 1.65–1.73 (m, 6H), 1.90 (ddd, *J* = 13.6, 8.9, 4.1, 1H), 2.31 (s, 1H), 2.37 (d, *J* = 13.4, 1H), 2.41–2.46 (m, 2H), 2.56–2.60 (m, 2H), 2.66 (d, *J* = 13.4, 1H), 3.72 (br s, 1H), 6.31 (br s, 1H). 13C-NMR (151 MHz, CDCl3): δ 19.18, 20.23, 24.16, 26.03, 28.43, 28.61, 37.58, 45.22, 47.88, 50.81, 56.47, 56.82, 58.03, 78.48, 157.80.
