4.8.2. Procedure B

A solution of hydrazine (75 mL, 1.5 mol) in EtOH (200 mL) was heated under reflux, and 1,3-dibromopropane (75 mL, 0.75 mol) was added slowly within 4 h. Stirring was continued for another hour, the solids were filtered off, washed with ethanol (3 × 50 mL), and discarded. The pH of the filtrate [combined with the EtOH washings and additional water (150 mL)] was adjusted to pH =3 by adding aqu. HBr (48% in water). Benzaldehyde (60 mL, 0.6 mol) was added, and the precipitate formed upon addition was filtered off, washed with water (3 × 50 mL), and discarded. The combined filtrates were extracted with ether (1000 mL), and the aq. The layer was concentrated under diminished pressure resulting in the formation of a red solid. Ethanol (250 mL) was added, and shaking of this suspension was continued for another 5 min. The yellowish solid was filtered off, washed with ethanol (250 mL) and ether (5 × 100 mL), and **8** (15.6 g, 7.5%) was obtained as a colorless solid; m.p. = 220–225 ◦C (lit.: [51,52] >250 ◦C); Rf = 0.8 (CHCl3:MeOH, 95:5); IR (ATR): *ν* = 2971*s*, 2728*s*, 2418*m*, 1577*s*, 1461*s*, 1331*m*, 1095*s*, 1027*m*, 890*m*, 696*m*, 547*m*, 491*m*, cm−1; 1H NMR (400 MHz, D2O): δ = 3.36–3.31 (*m*, 8H, 1-H, 3-H, 4-H, 6-H), 2.22–2.16 (*m*, 4H, 2-H, 5-H) ppm; 13C NMR (101 MHz, D2O): δ = 43.8 (C-1, C-3, C-4, C-6), 20.8 (C-2, C-5) ppm; MS (ESI, MeOH/CHCl3, 4:1): *m*/*z* = 115.0 (100%, [M+H-2 HBr]+).

#### *4.9. (3ß)28-(1,5-Diazocan-1-yl)-28-oxoolean-12-en-3-yl Acetate (14)*

Following GP 2 from 3-*O*-acetyl-oleanolic acid (9, 500 mg, 1.0 mmol), followed by chromatography (silica gel, CHCl3/MeOH (2% → 10%), compound **14** (425 mg, 71%) was obtained as a colorless solid; m.p. = 207–210 ◦C (decomp.); Rf = 0.52 (CHCl3/MeOH, 95:5); [*α*] 20 *<sup>D</sup>* = + 3.8◦ (*c* 0.088, CHCl3); IR (ATR): *ν* = 2954*m*, 1732*s*, 1626*m*, 1464*m*, 1368*s*, 1245*s*, 1026*s*, 750*s*, 662*w* cm−1; 1H NMR (400 MHz, CDCl3): δ = 5.25 (*m*, 1H, 12-H), 4.50 (*m*, 1H, 3-H), 3.67–3.11 (*m*, 8H, 33-H, 35-H, 36-H, 38-H), 3.03 (*d*, *J* = 13.8 Hz 1H, 18-H), 2.16–2.12 (m, 1H, 16-H), 2.04 (*s*, 3H, 32-H), 1.87–1.17 (*m*, 23H, 11-H, 34-H, 37-H, 19-Ha, 2-H, 1-Ha, 9-H, 6-Ha, 15-H, 7-H, 21-H, 6 Hb, 22-H, 19-Hb), 1.13 (*s*, 3H, 27-H), 1.01–0.98 (m, 1H, 1-Hb), 0.97-0.93 (*s*, 3H, 25-H), 0.92 (*s*, 3H, 30-H), 0.89 (*s*, 3H, 29-H), 0.85 (*s*, 3H, 23-H), 0.84 (*s*, 3H, 24-H), 0.82-0.81 (*m*, 1H, 5-H), 0.72 (*s*, 3H, 26-H) ppm; 13C NMR (101 MHz, CDCl3): δ = 177.0 (C-28), 171.2 (C-31), 144.7 (C-13), 121.7 (C-12), 81.1 (C-3), 55.5 (C-5), 47.9 (C-33, C-35, C-36, C-38), 47.8 (C-9),47.4 (C-17), 46.6 (C-19), 43.9 (C-18), 42.6 (C-14), 39.2 (C-8), 38.2 (C-1), 37.8 (C-4), 37.1 (C-10), 34.2 (C-21), 33.1 (C-7), 33.0 (C-29), 30.5 (C-34, C-37), 30.4 (C-20),29.8 (C-22), 28.2 (C-23), 27.6 (C-15), 26.0 (C-27), 24.1 (C-30), 23.7 (C-2), 23.5 (C-11), 22.8 (C-16), 21.4 (C-32), 18.3 (C-6), 17.3 (C-26), 16.8 (C-24), 15.6 (C-25) ppm; MS (ESI, MeOH/CHCl3, 4:1): *m*/*z* = 596.3 (100%, [M+H]+); analysis calcd. for C38H62N2O3 (594.93): C 76.72, H 10.50, N 4.71; found: C 76.47, H 10.74, N 4.50.
