1,2-Diiodoethane → HCID 68551037, compound

HRID 910003Notes

Reaction equation

HRID 910003 reaction equation
[Sm].ICCI.CN(C)P(N(C)C)(N(C)C)=O.[CH3:17][C:18]([Si:21]([CH3:46])([CH3:45])[O:22][C@@H:23]1[CH2:39][C:38]2[C@@:26]([CH3:44])([C@@H:27]3[C@@H:35]([CH2:36][CH:37]=2)[C@H:34]2[C@@:30]([CH3:43])([C@@H:31]([C:40](=[O:42])[CH3:41])[CH2:32][CH2:33]2)[CH2:29][CH2:28]3)[CH2:25][CH2:24]1)([CH3:20])[CH3:19].Br[CH2:48][CH2:49][CH2:50][CH2:51][CH:52]([CH3:54])[CH3:53]>O1CCCC1>[CH3:20][C:18]([Si:21]([CH3:46])([CH3:45])[O:22][C@@H:23]1[CH2:39][C:38]2[C@@:26]([CH3:44])([C@@H:27]3[C@@H:35]([CH2:36][CH:37]=2)[C@H:34]2[C@@:30]([CH3:43])([C@@H:31]([C@@:40]([OH:42])([CH2:48][CH2:49][CH2:50][CH2:51][CH:52]([CH3:54])[CH3:53])[CH3:41])[CH2:32][CH2:33]2)[CH2:29][CH2:28]3)[CH2:25][CH2:24]1)([CH3:17])[CH3:19]

Participants

7

Reactant 5

HCID 122241,2-DiiodoethaneHCID 12679HexamethylphosphoramideHCID 23951SamariumHCID 5207261-Bromo-5-methylhexaneHCID 108845053-tert-Butyldimethylsilyloxy Pregnenolone

Product 1

HCID 68551037HCID 68551037, compoundYield 57%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent4×

Procedure

To a stirred suspension of samarium metal (758 mg, 5.0 mmol) and 3 Å molecular sieves (0.5 g) in anhydrous tetrahydrofuran (THF, 9.5 mL) was slowly added a solution of 1,2-diiodoethane (1.3 g, 4.6 mmol) in THF (9.5 mL) at ambient temperature. After the reaction stirred for 30 min, hexamethylphosphoramide (HPMA, 3.0 mL, 17.2 mmol) was added to the reaction mixture and continued stirring for an additional 20 min. Then, a solution of ketone 1 (500.0 mg, 1.16 mmol) in THF (6.0 mL) was added followed by a solution of 1-bromo-5-methylhexane (208.0 mg, 1.16 mmol) in THF (2.0 mL). The reaction was allowed to stir for an additional hour until the starting material was completely consumed. After this, the reaction mixture was slowly treated with saturated NaHCO3, filtered through Celite and rinsed three times with an excess amount of diethyl ether. The filtrate was treated with water and extracted with diethyl ether. The ether extracts were washed with brine, dried over Na2SO4 and evaporated in vacuo to give a residue which was purified via silica gel chromatography. Elution with hexane-diethyl ether (4:1, v/v) afforded compound 2 (350.0 mg, 0.6 mmol, 57%) as a white powder (Honda et al. (1996) J. Chem. Soc., Perkin Trans. 1, 2291-2296).

Workup

  1. stirringcontinued stirring for an additional 20 min
  2. stirringto stir for an additional hour until the starting material
  3. customwas completely consumed
  4. additionAfter this, the reaction mixture was slowly treated with saturated NaHCO3
  5. filtrationfiltered through Celite
  6. washrinsed three times with an excess amount of diethyl ether
  7. additionThe filtrate was treated with water
  8. extractionextracted with diethyl ether
  9. washThe ether extracts were washed with brine
  10. dry with materialdried over Na2SO4
  11. customevaporated in vacuo
  12. customto give a residue which
  13. customwas purified via silica gel chromatography
  14. washElution with hexane-diethyl ether (4:1

Sources & evidence

ORD record
ord-d87c6319457d4abfb56c880842cf571f
Source dataset
uspto-grants-2011_09
Patent number
US08022052B2

Reaction notes

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