tert-Butyldimethylsilyl chloride → (1S,3aS,5R,7aR)-1-hydroxymethyl-5-(3-tert-butyldimethylsilyloxymethylphenyl)-7a-methylperhydroinden-3a,5-diol

HRID 725177

Reaktionsgleichung

Reaktionsgleichung von HRID 725177
[Si:1]([O:8][CH2:9][C:10]1[CH:11]=[C:12](Br)[CH:13]=[CH:14][CH:15]=1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].C([Si](C)(C)Cl)(C)(C)C.BrC1C=C(C=CC=1)CO.C([Li])CCC.[OH:39][CH2:40][C@@H:41]1[C@:49]2([CH3:50])[C@@:44]([OH:52])([CH2:45][C:46](=[O:51])[CH2:47][CH2:48]2)[CH2:43][CH2:42]1>C1COCC1.CCCCCC>[OH:39][CH2:40][C@@H:41]1[C@:49]2([CH3:50])[C@@:44]([OH:52])([CH2:45][C@:46]([C:12]3[CH:13]=[CH:14][CH:15]=[C:10]([CH2:9][O:8][Si:1]([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2])[CH:11]=3)([OH:51])[CH2:47][CH2:48]2)[CH2:43][CH2:42]1

Komponenten

8

Edukt 5

HCID 28928tert-Butyldimethylsilyl chlorideHCID 851413-Bromobenzyl alcoholHCID 220331471-Bromo-3-((((1,1-dimethylethyl)dimethylsilyl)oxy)methyl)benzeneHCID 22880913(1S,3aS,7aR)-1-hydroxymethyl-3a-hydroxy-7a-methyl-5-perhydroindenoneHCID 178418339Butyllithium

Produkt 1

HCID 11133585(1S,3aS,5R,7aR)-1-hydroxymethyl-5-(3-tert-butyldimethylsilyloxymethylphenyl)-7a-methylperhydroinden-3a,5-diolAusbeute 72 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 8028TetrahydrofuranLösungsmittel2×HCID 8058HexaneLösungsmittel

Reaktionsbedingungen

Temperatur
0 °C

Versuchsvorschrift

To a suspension of 60.0 g of 3-(tert-butyldimethylsilyloxymethyl)bromobenzene (prepared from tert-butyldimethylchlorosilane and 3-bromobenzyl alcohol according to the procedure described by Kendall P. M. et al., J. Org. Chem., 1979, 44, 1421) in 500 ml of anhydrous THF cooled to -78° C., 131 ml of 1.6M n-butyllithium in n-hexane were added under a nitrogen atmosphere and the resulting mixture was stirred for 2.5 hrs. A solution of 6.30 g of (1S,3aS,7aR)-1-hydroxymethyl-3a-hydroxy-7a-methyl-5-perhydroindenone in 60 ml of anhydrous THF was added. After 1 hr the reaction mixture was allowed to warm to 0° C., and cautiously quenched with 300 ml of 5% aqueous NaH2PO4.H2O and extracted with ethyl acetate. The organic layer was dried over sodium sulfate and evaporated to dryness under reduced pressure. The residue was purified by flash-chromatography (SiO2) with n-hexane/acetone/chloroform 6:2:2 as the eluant to give 9.62 g of (1S,3aS,5R,7aR)-1-hydroxymethyl-5-(3-tert-butyldimethylsilyloxymethylphenyl)-7a-methylperhydroinden-3a,5-diol as a white foam.

Aufarbeitung

  1. waitAfter 1 hr the reaction mixture was allowed
  2. customcautiously quenched with 300 ml of 5% aqueous NaH2PO4.H2O
  3. extractionextracted with ethyl acetate
  4. dry with materialThe organic layer was dried over sodium sulfate
  5. customevaporated to dryness under reduced pressure
  6. customThe residue was purified by flash-chromatography (SiO2) with n-hexane/acetone/chloroform 6:2:2 as the eluant

Quellen und Nachweise

ORD-Eintrag
ord-b81f760848504a3a937cb3f63d494903
Quelldatensatz
uspto-grants-1998_01
Patentnummer
US05705531

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