## Materials and Methods
### Synthetic Procedures
#### 2.2.2 Synthesis of 16-Cyano-3\(\beta\)-Hydroxy-Androst-5-en-17-One (**3**)
\({}^{1}\)H NMR (DMSO-\(d_{6}\), 500 MHz): \(\delta\) 0.96 (s, 3H, 18-H\({}_{3}\)), 1.01 (s, 3H, 19-H\({}_{3}\) and m, 2H), 1.37 (m, 1H), 1.50-1.80 (overlapping m, 8H), 1.97-2.20 (overlapping m, 5H), 2.41 (dd, 1H, \(J\) = 13.3 Hz, \(J\) = 4.7 Hz, one of 15-H\({}_{2}\)), 3.27 (m, 1H, 3-H), 4.63 (d, 1H, \(J\) = 4.5 Hz, 3-OH), 5.11 (s, 2H, 5\"-NH\({}_{2}\)), 5.32 (m, 1H, 6-H), 7.23 (dd, 2H, \(J\) = 8.8 Hz, \(J\) = 8.8 Hz, 3\"-H and 5\"-H), 7.54 (dd, 2H, \(J\) = 8.8 Hz, \(J\) = 5.0 Hz, 2\"-H and 6\"-H); \({}^{13}\)C NMR (DMSO-\(d_{6}\), 125 MHz): \(\delta\) 18.0 (C-18), 19.1 (C-19), 20.2 (CH\({}_{2}\)), 23.6 (CH\({}_{2}\)), 30.4 (CH), 30.9 (CH\({}_{2}\)), 31.5 (CH\({}_{2}\)), 33.5 (CH\({}_{2}\)), 33.5 (CH\({}_{2}\)), 36.4 (C-10), 36.9 (CH\({}_{2}\)), 40.3 (C-13), 42.3 (CH\({}_{2}\)), 50.1 (CH), 61.2 (CH), 70.0 (C-3), 104.1 (C-16), 115.5 (d, 2C, \(J\) = 22.5 Hz, C-3\" and C-5\"), 120.2 (C-6), 124.5 (d, 2C, \(J\) = 8.4 Hz, C-2\" and C-6\"), 136.7 (d, \(J\) = 2,5 Hz, C-1\"), 140.8 (C-5), 141.6 (C-5\"), 159.6 (d, \(J\) = 241.9 Hz, C-4\"), 168.4 (C-17); ESI-MS 422 [M + H]\({}^{+}\). 5\({}^{\prime}\)-Amino-1\({}^{\prime}\)-(4\"-Chloro)phenylpyrazolo[3\({}^{\prime}\),\({}^{\prime}\)4\({}^{\prime}\):17,16]Androst-5-en-3\(\beta\)-ol (**6e**)  
4-Chloro-phenylhydrazine hydrochloride (**5e**, 134 mg) was used as described in the general procedure. Yield: 175 mg (80%, white solid); Mp 299-301 \({}^{\circ}\)C; \(R_{\rm f}\) = 0.32 (EtOAc/CH\({}_{2}\)Cl\({}_{2}\) = 20:80 _v_/_v_). Anal. Calcd. for C\({}_{26}\)H\({}_{32}\)CN\({}_{3}\)O (438.01): C, 71.30; H, 7.36. Found: C, 71.45; H, 7.22. \({}^{1}\)H NMR (DMSO-\(d_{6}\), 500 MHz): \(\delta\) 0.96 (s, 3H, 18-H\({}_{3}\)), 1.01 (s, 3H, 19-H\({}_{3}\) and m, 2H), 1.36 (m, 1H), 1.50-1,80 (overlapping m, 8H), 1.98-2,19 (overlapping m, 5H), 2.41 (dd, 1H, \(J\) = 13.4 Hz, \(J\) = 4.5 Hz, one of 15-H\({}_{2}\)), 3.27 (m, 1H, 3-H), 4.63 (d, 1H, \(J\) = 4.5 Hz, 3-OH), 5.19 (s, 2H, 5\"-NH\({}_{2}\)), 5.32 (m, 1H, 6-H), 7.44 (d, 2H, \(J\) = 8.8 Hz, 3\"-H and 5\"-H), 7.58 (d, 2H, \(J\) = 8.8 Hz, 2\"-H and 6\"-H); \({}^{13}\)C NMR (DMSO-\(d_{6}\), 125 MHz): \(\delta\) 17.9 (C-18), 19.2 (C-19), 20.2 (CH\({}_{2}\)), 23.6 (CH\({}_{2}\)), 30.4 (CH), 30.9 (CH\({}_{2}\)), 31.5 (CH\({}_{2}\)), 33.4 (CH\({}_{2}\)), 36.4 (C-10), 36.8 (CH\({}_{2}\)), 40.3 (C-13), 42.3 (CH\({}_{2}\)), 50.0 (CH), 61.1 (CH), 70.0 (C-3), 104.6 (C-16), 117.2 (C-4\"), 120.2 (C-6), 124.0 (2C, C-2\" and C-6\"), 131.7 (2C, C-3\" and C-5\"), 139.6 (C-1\"), 141.0 (C-5\"), 141.6 (C-5\"), 168.9 (C-17); ESI-MS 483 [M + H 4-Cyano-phenylhydrazine hydrochloride (**5g**, 127 mg) was used as described in the general procedure. Yield: 182 mg (85%, white solid); Mp 293-295 \({}^{\circ}\)C; \(R_{\rm f}\) = 0.34 (EtOAc/CH\({}_{2}\)Cl\({}_{2}\) = 20:80 \(v\)/\(v\)). Anal. Calcd. for C\({}_{2}\)H\({}_{32}\)N\({}_{4}\)O (428.58): C, 75.67; H, 7.53. Found: C, 75.75; H, 7.39. \({}^{\dagger}\)H NMR (DMSO-\(d_{6}\), 500 MHz): \(\delta\) 0.97 (s, 3H, 18-H\({}_{3}\)), 1.01 (s, 3H, 19-H\({}_{3}\) and m, 2H), 1.36 (m, 1H), 1.51-1.79 (overlapping m, 8H), 1.97-2.20 (overlapping m, 5H), 2.43 (dd, 1H, \(J\) = 13.6 Hz, \(J\) = 4.7 Hz, one of 15-H\({}_{2}\)), 3.27 (m, 1H, 3-H), 4.63 (d, 1H, \(J\) = 4.5 Hz, 3-OH), 5.32 (m, 1H, 6-H), 5.40 (s, 2H, 5'-NH\({}_{2}\)), 7.82 (d, 2H, \(J\) = 8.7 Hz, 3\"-H and 5\"-H), 7.85 (d, 2H, \(J\) = 8.7 Hz, 2\"-H and 6\"-H); \({}^{13}\)C NMR (DMSO-\(d_{6}\), 125 MHz): \(\delta\) 17.8 (C-18), 19.1 (C-19), 20.1 (CH\({}_{2}\)), 23.5 (CH\({}_{2}\)), 30.4 (CH), 30.8 (CH\({}_{2}\)), 31.5 (CH\({}_{2}\)), 33.3 (CH\({}_{2}\)), 36.3 (C-10), 36.8 (CH\({}_{2}\)), 40.3 (C-13), 42.3 (CH\({}_{2}\)), 50.0 (CH), 61.0 (CH), 70.0 (C-3), 105.7 and 106.2: C-4\" and C-16, 118.9 (4\"-CN), 120.1 (C-6), 121.2 (2C, C-2\" and C-6\"), 133.2 (2C, C-3\" and C-5\"), 141.6 and 141.7: C-1\" and C-5, 144.2 (C-5'), 170.1 (C-17); ESI-MS 429 [M + H]\({}^{+}\). 5'-Amino-1'-(4\"-Nitro)phenylpyrazol[3',4':17,16]Androst-5-en-3\(\beta\)-ol (**6h**)  
4-Nitro-phenylhydrazine hydrochloride (**5h**, 127 mg) was used as described in the general procedure.