Sodium hydride → HCID 67301139, compound

HRID 1014974Notes

Reaction equation

HRID 1014974 reaction equation
[Si:1]([O:8][C@@H:9]1[C@@:28]2([CH3:29])[C:13](=[CH:14][CH:15]=[C:16]3[C@@H:27]2[CH2:26][CH2:25][C@@:24]2([CH3:30])[C@H:17]3[CH2:18][CH:19]=[C:20]2[C@H:21]([OH:23])[CH3:22])[CH2:12][C@@H:11]([O:31][Si:32]([C:35]([CH3:38])([CH3:37])[CH3:36])([CH3:34])[CH3:33])[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[H-].[Na+].C1OCCOCCOCCOCCOC1.Br[CH2:57][C:58]([O:60][C:61]([CH3:64])([CH3:63])[CH3:62])=[O:59]>O1CCCC1>[Si:1]([O:8][C@@H:9]1[C@@:28]2([CH3:29])[C:13](=[CH:14][CH:15]=[C:16]3[C@@H:27]2[CH2:26][CH2:25][C@@:24]2([CH3:30])[C@H:17]3[CH2:18][CH:19]=[C:20]2[C@H:21]([O:23][CH2:57][C:58]([O:60][C:61]([CH3:64])([CH3:63])[CH3:62])=[O:59])[CH3:22])[CH2:12][C@@H:11]([O:31][Si:32]([C:35]([CH3:37])([CH3:36])[CH3:38])([CH3:33])[CH3:34])[CH2:10]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 24758Sodium hydrideHCID 3633615-Crown-5HCID 79177tert-Butyl bromoacetateHCID 120200831alpha,3beta-bis(tert-butyldimethylsilyloxy)-20(R)-hydroxypregna-5,7,16-triene

Product 1

HCID 67301139HCID 67301139, compoundYield 75%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

1α,3β-Bis(tert-butyldimethylsilyloxy)-20(R)-hydroxypregna-5,7,16-triene (158 mg, 0.283 mmol) was treated with sodium hydride (60% in oil, 77 mg, 1.925 mmol), tetrahydrofuran (6 ml), 15-crown-5 (67 mg, 0.304 mmol) and t-butyl bromoacetate (0.25 ml, 1.679 mmol) in the same manner as shown in Example 8(1) (at an external temperature of 85° C. for 11 hours and 40 minutes) and then worked up. The resulting residue was purified by column chromatography (hexane:ethyl acetate=10:1) and preparative thin layer chromatography (0.5 mm×3 plates, hexane:ethyl acetate=20:1, developed twice) to give the titled compound (142.6 mg, 75%) as a colorless oil.

Workup

  1. customat an external temperature of 85° C.
  2. customfor 11 hours
  3. custom40 minutes
  4. customThe resulting residue was purified by column chromatography (hexane:ethyl acetate=10:1) and preparative thin layer chromatography (0.5 mm×3 plates, hexane

Sources & evidence

ORD record
ord-35e7f1e3100b445a911050f9ad816422
Source dataset
uspto-grants-2011_07
Patent number
US07985744B2

Reaction notes

Loading…