CH and CH2, 14H), 2.82 (m, 2H, 6-CH2), 2.89 (s, 6H, (CH3)2N), 3.01 (m, 2H, 17α-CH2N) 5.02 (s, 2H,
OCH2Ph), 5.10 (m, 1H, NH), 6.70 (d, J = 2.4 Hz, 1H, 4-CH), 6.75 (dd, J1 = 2.5 Hz, J2 = 8.1 Hz, 1H, 2-
CH), 7.12 (d, J = 8.6 Hz, 1H, 1-CH), 7.20 (d, J = 7.5 Hz, 1H, 7’-CH), 7.40 (m, 5H, Ph), 7.56 (m, 2H,
3’-CH and 8’-CH), 8.25 (d, J = 7.2 Hz, 1H, 2’-CH), 8.31 (d, J = 8.6 Hz, 1H, 9’-CH), 8.55 (d, J = 8.5 Hz,
1H, 4’-CH). 13C NMR (Acetone-d6) δ: 13.7, 22.9, 26.1, 27.2, 31.5, 33.3, 39.6, 43.5, 44.7 (2C), 46.0, 49.5,
49.6, 49.8, 69.3, 81.9, 112.2, 114.6, 115.2, 119.5, 123.3, 126.1, 127.4 (2C), 127.6, 127.9, 128.3 (2C),
128.8, 129.7, 129.8, 129.9, 132.6, 136.2, 137.7, 137.9, 151.9, 156.7. HRMS: for C38H45N2O4S [M + H]+:
625.3095 (calculated), 625.3090 (found).
2.3.4 (8β,9α,14α,17β)-17-({[5-(dimethylaminonaphthalen-1-yl)sulfonyl]amino}methyl)estra-1,3,5(10)-
triene-3,17-diol (7)
A mixture of dansyl derivative 6 (450 mg, 0.72 mmol) and 10% palladium on charcoal (225 mg)
in MeOH/AcOH (75:25) (30 mL) was stirred for 2 h under hydrogen atmosphere. The palladium reagent
was then removed by filtration on celite, washed with MeOH, and the filtrate was evaporated under
reduced pressure. Purification by flash chromatography using hexanes/EtOAc (7:3) as eluent afforded
compound 7 (335 mg, 55%) as a light green fluorescent amorphous solid. IR (film) : 3448 and 3333
(OH and NH2).1H NMR (Acetone-d6) δ: 0.87 (s, 3H, 18-CH3), 1.18-2.20 (unassigned CH and CH2, 13H),
2.73 (m, 2H, 6-CH2), 2.88 (s, 6H, (CH3)2N), 3.02 (m, 2H, 17α-CH2N), 3.58 (s, 1H, OH), 6.16 (m, 1H,
NH), 6.51 (s, 1H, 4-CH), 6.57 (dd, J1 = 8.4 Hz, J2 = 2.6 Hz, 1H, 2-CH), 7.02 (d, J = 8.4 Hz, 1H, 1-CH),
7.28 (d, J = 7.5 Hz, 1H, 7’-CH), 7.63 (m, 2H, 3’-CH and 8’-CH), 7.89 (s, 1H, OH), 8.24 (dd, J1 = 7.3
Hz, J2 = 0.8 Hz, 1H, 2’-CH), 8.45 (d, J = 8.7 Hz, 1H, 9’-CH), 8.57 (d, J = 8.5 Hz, 1H, 4’-CH). 13C NMR
(Acetone-d6) δ: 13.8, 22.9, 26.1, 27.3, 29.4, 31.5, 33.3, 39.7, 43.5, 44.7 (2C), 46.0, 49.6, 49.8, 82.0, 112.6,
114.9, 115.2, 119.5, 123.3, 126.1, 127.9, 128.8, 129.7, 129.8, 129.9, 131.0, 136.1, 137.5, 151.9, 155.0.
HRMS for C31H39N2O4S [M+H]+: 535.2625 (calculated), 535.2633 (found). HPLC purity: 95.2% (RT =
12.9 min; Alltima HP18 reversed-phase column (250 mm x 4.6 mm, 5 µm); solvent gradient of
MeOH/H2O from 70:30 to 100:0).
2.3.5
(8β,9α,14α,17β)-17-({[5-(dimethylaminonaphthalen-1-yl)sulfonyl]amino}methyl)-17-hydroxy
estra-1,3,5(10)-trien-3-yl sulfamate (8)
7