Synthesis of Cyclic Amine Diastereomers

In the glovebox, gold precatalyst 7 (6.3 mg, 0.010 mmol, 15 mol %) was dissolved in 0.3 mL dry DCM and added to a dram vial containing NaBArF salt 8 (9.2 mg, 0.010 mmol, 15 mol %). The resulting suspension was added to a screw-cap dram vial containing aziridine 1b (18 mg, 0.069 mmol, 1.0 equiv). A single 0.3 mL portion of DCM was used to rinse the two vials formerly containing the gold precatalyst and the NaBArF salt to aid in complete transfer to the aziridine vial. Finally, Pd₂dba₃ (4.8 mg, 0.0052 mmol, 7.5 mol %) was added to the aziridine mixture as a solution in 0.3 mL DCM. The reaction vessel was capped and stirred at 25 °C in the glovebox 5 d. The crude reaction mixture was then removed from the glovebox and concentrated in vacuo. The mixture was purified using a silica gel pipet column eluting using a gradient 1:0:99 to 1:5:94 NH₄OH:MeOH:CHCl₃. The product was obtained as a mixture of diastereomers (16 mg, 88% yield, d.r. = 1.0 : 1.0). Diastereomer A. ¹H NMR (CDCl₃, 500 MHz): δ 1.69–1.99 (m, 14 H), 2.06 (dd, J = 13.0, 6.6 Hz), 2.59–2.64 (m, 1H), 2.85 (J = 14.0, 7.3 Hz, 1H), 3.20–3.26 (m, 1H), 3.29 (d, J = 13.9 Hz, 1H), 3.81 (t, J = 10.0 Hz, 1H), 4.02 (dd, J = 12.1, 6.7 Hz, 1H), 4.84 (d, J = 13.7 Hz, 1H), 5.03 (q, J = 9.4 Hz, 1H), 5.22 (d, J = 10.3 Hz, 1H), 5.28 (d, J = 17.2 Hz, 1H), 5.78–5.88 (m, 2H). Diastereomer B. 1.69–1.99 (m, 14 H), 2.12 (dd, J = 13.8, 6.5 Hz, 1H), 2.57 (d, J = 8.4 Hz, 1H), ca. 2.79 (dd, 1H), c.a. 3.31 (1H), 3.54–5.63 (m, 1H), 3.85 (d, J = 13.6 Hz, 1H), 4.06 (d, J = 13.4 Hz, 1H), 4.63 (dd, J = 12.9, 8.1 Hz, 1H), 5.08 –5.14 (m, 1H), 5.17–5.25 (m, 2H), 5.70 (d, J = 9.8 Hz, 1H), 6.16 (d, J = 9.9 Hz, 1H). ¹³C NMR (CDCl₃, 125 MHz): 26.8, 26.9, 33.4, 33.4, 33.7, 35.0, 37.0, 39.4, 40.0, 42.6, 49.3, 68.4, 70.6, 72.4, 76.7, 119.3, 133.3. Note: Not all signals were observable. HRMS (GC/EI+): [M]⁺ calcd for C₁₈H₂₇N, 257.2144; found, 257.2137.