p-Toluenesulfonic acid → 3-(Benzyloxy)estra-1,3,5(10),15-tetraen-17-one

HRID 1744213Notes

Reaction equation

HRID 1744213 reaction equation
[CH2:1]([O:8][C:9]1[CH:26]=[CH:25][C:24]2[C@@H:23]3[C@H:14]([C@H:15]4[C@@:19]([CH2:21][CH2:22]3)([CH3:20])[C:18]3(OCC[O:27]3)[CH:17]=[CH:16]4)[CH2:13][CH2:12][C:11]=2[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.CC1C=CC(S(O)(=O)=O)=CC=1.C([O-])(O)=O.[Na+]>CC(C)=O.O>[CH2:1]([O:8][C:9]1[CH:26]=[CH:25][C:24]2[C@@H:23]3[C@H:14]([C@H:15]4[C@@:19]([CH2:21][CH2:22]3)([CH3:20])[C:18](=[O:27])[CH:17]=[CH:16]4)[CH2:13][CH2:12][C:11]=2[CH:10]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 516892Sodium BicarbonateHCID 68616725(8R,9S,13S,14S)-3-(Benzyloxy)-13-methyl-6,7,8,9,11,12,13,14-octahydrospiro[cyclopenta[a]phenanthrene-17,2'-[1,3]dioxolane]

Product 1

HCID 150979713-(Benzyloxy)estra-1,3,5(10),15-tetraen-17-oneYield 51,776.102%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 962WaterSolvent

Procedure

A solution of 1.04 g (2.57 mmol) of 43, 117 mg (0.617 mmol) of pTsOH in acetone (70.3 mL) and H2O (11.4 mL) was stirred at rt for 1.5 h. The reaction mixture was adjusted to pH 7 with 5% NaHCO3 and concentrated by rotovap to about 30 mL without heating. The solution was poured into H2O (50 mL) and extracted with EtOAc (3×, 70 mL). Combined organic extracts were dried over Na2SO4 and concentrated in vacuo giving a white solid. Crystallization of the residue from CH2Cl2/hexanes gave 477 g (52%) of 44 as fine white needles. Data for 44: TLC, T-1, Rf 0.5; 1H NMR (400 MHz, CDCl3) δ 1.12 (s, 3H, H-18), 5.05 (s, 2H, benzylic-H), 6.10 (dd, 1H, J=5.9, 3.2 Hz, H-15), 6.76 (d, 1H, J=2.7 Hz, H-4), 6.81 (dd, 1H, J=8.6, 2.7 Hz, H-2), 7.22 (d, 1H, J=8.6 Hz, H-1), 7.31–7.45 (m, 5H, Ar—H), 7.64 (dd, 1H, J=5.9, 1.1 Hz, H-16).

Workup

  1. concentrationconcentrated by rotovap to about 30 mL
  2. temperaturewithout heating
  3. additionThe solution was poured into H2O (50 mL)
  4. extractionextracted with EtOAc (3×, 70 mL)
  5. dry with materialCombined organic extracts were dried over Na2SO4
  6. concentrationconcentrated in vacuo
  7. customgiving a white solid
  8. customCrystallization of the residue from CH2Cl2/hexanes

Sources & evidence

ORD record
ord-217b821cc8df48e68fea56aafcb6540f
Source dataset
uspto-grants-2006_03
Patent number
US07015211B2

Reaction notes

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