Iodine → (3alpha,5alpha)-3-(Acetyloxy)-20-oxo-pregnane-18-carbonitrile

HRID 408105Notes

Reaction equation

HRID 408105 reaction equation
II.C([O-])([O-])=O.[Ca+2].[C:8]([O:11][C@@H:12]1[CH2:31][CH2:30][C@@:29]2([CH3:32])[C@@H:14]([CH2:15][CH2:16][C@@H:17]3[C@@H:28]2[CH2:27][CH2:26][C@@:25]2([CH3:33])[C@H:18]3[CH2:19][CH2:20][C@@H:21]2[C:22](=[O:24])[CH3:23])[CH2:13]1)(=[O:10])[CH3:9].[C:34]([O:37][C@@H:38]1[CH2:59][CH2:58][C@@:57]2([CH3:60])[C@@H:40]([CH2:41][CH2:42][C@@H:43]3[C@@H:56]2[CH2:55][CH2:54][C@@:53]2([CH3:61])[C@H:44]3[CH2:45][CH2:46][C@@H:47]2[C:48]([OH:52])([C:50]#[N:51])[CH3:49])[CH2:39]1)(=[O:36])[CH3:35]>C1CCCCC1>[C:8]([O:11][C@@H:12]1[CH2:31][CH2:30][C@@:29]2([CH3:32])[C@@H:14]([CH2:15][CH2:16][C@@H:17]3[C@@H:28]2[CH2:27][CH2:26][C@@:25]2([CH2:33][C:50]#[N:51])[C@H:18]3[CH2:19][CH2:20][C@@H:21]2[C:22](=[O:24])[CH3:23])[CH2:13]1)(=[O:10])[CH3:9].[C:34]([O:37][C@@H:38]1[CH2:59][CH2:58][C@@:57]2([CH3:60])[C@@H:40]([CH2:41][CH2:42][C@@H:43]3[C@@H:56]2[CH2:55][CH2:54][C@@:53]2([CH3:61])[C@H:44]3[CH2:45][CH2:46][C@@H:47]2[C:48](=[O:52])[CH3:49])[CH2:39]1)(=[O:36])[CH3:35]

Participants

7

Reactant 4

HCID 807IodineHCID 10112Calcium CarbonateHCID 11463359(3alpha,5alpha)-3-(Acetyloxy)-20-hydroxypregnane-20-carbonitrileHCID 53835422Allopregnan-3alpha-ol-20-one acetate

Product 2

HCID 11246136(3alpha,5alpha)-3-(Acetyloxy)-20-oxo-pregnane-18-carbonitrileHCID 53835422Allopregnan-3alpha-ol-20-one acetate

Reagents, catalysts & solvents 1

HCID 8078CyclohexaneSolvent

Procedure

Compound 8a was prepared using a reported procedure. (See, Kalvoda, J., et al., Reactions of Steroid Hypoiodites. VII. 1,4-Shift of the Nitrile Group (18-Cyanopregnanes), Helv. Chim. Acta 1966, 49: 424-436) I2 (1.6 g, 6.30 mmol) was added to a refluxing mixture of Pb(OAc)4 (6.0 g, 13.5 mmol) and CaCO3 (2 g, 20.0 mmol) in cyclohexane (200 mL). The purple solution was refluxed for 1 h and the mixture of compound 6a and 7a obtained in last step [prepared from 6a (1.0 g, 2.77 mmol)] was added. The reaction mixture was refluxed while irradiated with a 300 W tungsten lamp for 3 h and then cooled to room temperature. After filtration, the precipitate was washed thoroughly with ether. The combined filtrate was washed successively with 10% Na2S2O3 and brine, and dried over Na2SO4. Removal of solvent under reduced pressure gave a residue which was purified by column chromatography (silica gel; hexanes/EtOAc, 4:1) to give compound 8a (400 mg, 40% from 6a) and recovered compound 6a (400 mg).

Workup

  1. temperatureThe purple solution was refluxed for 1 h

Sources & evidence

ORD record
ord-9252e084d6fa412e90eeebf2a5c9b81b
Source dataset
uspto-grants-2014_06
Patent number
US08759330B2

Reaction notes

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