## Materials and Methods
### Synthetic Procedures
#### 2.2.2 Synthesis of 16-Cyano-3\(\beta\)-Hydroxy-Androst-5-en-17-One (**3**)  
To a solution of compound 2 (2 g, 6.03 mmol) in MeOH (20 mL), KOH (1.68 g, 30 mmol), also dissolved in MeOH (10 mL) was added. After stirring the mixture at room temperature for 30 min,it was poured into water (100 mL) and neutralized with diluted HCl. The precipitate was filtered off and dried. Column chromatographic purification of the crude product with EtOAc/CH\({}_{2}\)Cl\({}_{2}\) = 10:90 provided an epimeric mixture (16\(\beta\)-CN (a)/16\(\alpha\)-CN (b) = 2:1) of 3 as a white solid (1.64 g, 87\(\%\)). \(R_{\rm f}\) = 0.48. Anal. Calcd. for C\({}_{20}\)H\({}_{27}\)NO\({}_{2}\) (313.44): C, 76.64; H, 8.68. Found: C, 76.55; H, 8.59. \({}^{1}\)H NMR (DMSO-\(d_{6}\), 500 MHz): \(\delta\) 0.88 (s, 18-H\({}_{3}\), b), 0.90 (s, 18-H\({}_{3}\), a), 0.96 (s, 19-H\({}_{3}\), a + b), 3.26 (m, 3-H, a + b), 3.78 (dd, \(J\) = 9.3 Hz, \(J\) = 9.3 Hz, 16-H, a), 4.36 (d, \(J\) = 8.7 Hz, 16-H, b), 4.63 (d, \(J\) = 4.4 Hz 3-OH, a + b), 5.30 (m, 6-H, a + b); \({}^{13}\)C NMR (DMSO-\(d_{6}\), 125 MHz): \(\delta\) 12.8 (C-18, b), 13.7 (C-18, a), 19.1 (C-19, a + b), 19.7 (CH\({}_{2}\), a + b), 26.9 (CH\({}_{2}\), b), 27.5 (CH\({}_{2}\), a), 29.7 (CH\({}_{2}\), b), 30.1 (CH\({}_{2}\), a), 30.4 (CH, a), 30.9 (CH, b), 30.9 (CH\({}_{2}\), a), 31.1 (CH\({}_{2}\), b), 31.4 (CH\({}_{2}\), a + b), 35.3 (CH, b), 36.2 (C-10, a + b), 36.3 (CH, a), 36.8 (CH\({}_{2}\), a + b), 42.1 (C-13, a + b), 47.0 (CH\({}_{2}\), b), 47.6 (CH\({}_{2}\), a), 48.3 (CH, a + b), 49.2 (CH, b), 49.5 (CH, a), 69.9 (C-3, a + b), 118.4 (CN, a), 118.6 (CN, a), 119.7 (C-6, a), 119.8 (C-6, b), 141.4 (C-5, b), 141.5 (C-5, a), 209.3 (C-17, b), 209.5 (C-17, a); ESI-MS 314 [M + H]\({}^{+}\). 2.3 General Procedure for The Synthesis of D-Ring-Condensed 5-Amino-1-Arylpyrazoles (6a-h) Under MW Irradiation  
To a solution of 16-cyano-3\(\beta\)-hydroxy-androst-5-en-17-one (3, 157 mg, 0.5 mmol) in EtOH (5 mL), arylhydrazine hydrochloride (5a-h, 1.5 equiv., 0.75 mmol) and NaOAc (61.5 mg, 1.5 equivalent) were added, and the mixture was MW-irradiated at 120 \({}^{\circ}\)C for 10 min in a closed vessel. After completion of the reaction, the mixture was poured into water (20 mL), saturated with NH\({}_{4}\)Cl and the precipitate formed was filtered off. Column chromatographic purification of the crude product was performed with EtOAc/CH\({}_{2}\)Cl\({}_{2}\) = 20:80 as mobile phase. 5\({}^{\prime}\)-Amino-1\({}^{\prime}\)-Phenylpyrazolo[3\({}^{\prime}\),\({}^{\prime}\):17,16]Androst-5-en-3\(\beta\)-ol (6a)  
Phenylhydrazine hydrochloride (5a, 108 mg) was used as described in the general procedure. Yield: 182 mg (90\(\%\), white solid); Mp 258-260 \({}^{\circ}\)C; \(R_{\rm f}\) = 0.23 (EtOAc/CH\({}_{2}\)Cl\({}_{2}\) = 20:80 \(v\)/\(v\)). Anal. Calcd. for C\({}_{26}\)H\({}_{33}\)N\({}_{3}\)O (403.57): C, 77.38; H, 8.24. Found: C, 77.27; H, 8.13. \({}^{1}\)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), 1.37 (m, 1H), 1.51-1.81 (overlapping m, 8H), 1.96-2.20 (overlapping m, 5H), 2.42 (dd, 1H, \(J\) = 13.3 Hz, \(J\) = 5.0 Hz, one of 15-H\({}_{2}\)), 3.28 (m, 1H, 3-H), 4.62 (d, 1H, \(J\) = 3.0 Hz, 3-OH), 5.09 (s, 2H, 5'-NH\({}_{2}\)), 5.33 (d, 1H, \(J\) = 4.5 Hz, 6-H), 7.21 (m, 1H, 4\"-H), 7.41 (m, 2H, 3\"-H and 5\"-H), 7.54 (d, 2H, \(J\) = 7.7 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\({}_{2}\)), 36.3 (C-10), 36.8 (CH\({}_{2}\)), 40.2 (C-13), 42.3 (CH\({}_{2}\)), 50.1 (CH), 61.2 (CH), 70.0 (C-3), 104.1 (C-16), 120.2 (C-6), 122.2 (2C, C-2\" and C-6\"), 125.0 (C-4\"), 128.8 (2C, C-3\" and C-5\"), 140.3, 140.6 and 140.7 (C-5, C-5' and C-1\"), 168.4 (C-17); ESI-MS 404 [M + H]\({}^{+}\).