1,2-Diiodoethane → (3S,8S,9S,10R,13S,14S,17S)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-3-[(1,1-dimethylethyl)dimethylsilyloxy]-17-((S)-2-hydroxy-7-methyloctan-2-yl)-10,13-dimethyl-1H-cyclopenta[a]phenanthrene

HRID 910003Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 910003
[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]

Komponenten

7

Edukt 5

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

Produkt 1

HCID 68551037(3S,8S,9S,10R,13S,14S,17S)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-3-[(1,1-dimethylethyl)dimethylsilyloxy]-17-((S)-2-hydroxy-7-methyloctan-2-yl)-10,13-dimethyl-1H-cyclopenta[a]phenanthreneAusbeute 57 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel4×

Versuchsvorschrift

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).

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-d87c6319457d4abfb56c880842cf571f
Quelldatensatz
uspto-grants-2011_09
Patentnummer
US08022052B2

Notizen zur Reaktion

Wird geladen…