(3R,5R)-3,5-Bis[(tert-butyldimethylsilyl)oxy]-1-hydroxy4-methylenecyclohexanecarboxylic Acid Methyl Ester → [(3R,5R)-3,5-Bis[(tert-butyldimethylsilyl)oxy]-1-hydroxy4-methylenecyclohexyl]methanol

HRID 10164Notes

Reaction equation

HRID 10164 reaction equation
[H-].C([Al+]CC(C)C)C(C)C.C[O:12][C:13]([C:15]1([OH:38])[CH2:20][C@@H:19]([O:21][Si:22]([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:24])[CH3:23])[C:18](=[CH2:29])[C@H:17]([O:30][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:33])[CH3:32])[CH2:16]1)=O>CCOCC>[Si:22]([O:21][C@H:19]1[C:18](=[CH2:29])[C@H:17]([O:30][Si:31]([C:34]([CH3:37])([CH3:36])[CH3:35])([CH3:33])[CH3:32])[CH2:16][C:15]([CH2:13][OH:12])([OH:38])[CH2:20]1)([C:25]([CH3:27])([CH3:28])[CH3:26])([CH3:24])[CH3:23]

Participants

4

Reactant 2

HCID 10502782(3R,5R)-3,5-Bis[(tert-butyldimethylsilyl)oxy]-1-hydroxy4-methylenecyclohexanecarboxylic Acid Methyl EsterHCID 21225700Diisobutylaluminumhydride

Product 1

HCID 10787320[(3R,5R)-3,5-Bis[(tert-butyldimethylsilyl)oxy]-1-hydroxy4-methylenecyclohexyl]methanolYield 24%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
-24 °C

Procedure

Diisobutylaluminum hydride (1.5 M in toluene, 2.0 mL, 3 mmol) was added to a solution of the ester 3 (215 mg, 0.5 mmol) in anhydrous ether (3 mL) at −78° C. under argon. The mixture was stirred at −78° C. for 3 h and at −24° C. for 1.5 h, diluted with ether (10 mL) and quenched by the slow addition of 2N potassium sodium tartrate. The solution was warmed to room temperature and stirred for 15 min, then poured into brine and extracted with ethyl acetate and ether. The organic extracts were combined, washed with diluted (ca. 1%) HCl, and brine, dried (MgSO4) and evaporated. The crystalline residue was purified by flash chromatography. Elution with hexane/ethyl acetate (9:1) gave crystalline diol 4 (43 mg, 24%).

Workup

  1. customquenched by the slow addition of 2N potassium sodium tartrate
  2. temperatureThe solution was warmed to room temperature
  3. stirringstirred for 15 min
  4. additionpoured into brine
  5. extractionextracted with ethyl acetate and ether
  6. washwashed
  7. additionwith diluted (ca. 1%) HCl, and brine
  8. dry with materialdried (MgSO4)
  9. customevaporated
  10. customThe crystalline residue was purified by flash chromatography
  11. washElution with hexane/ethyl acetate (9:1)

Sources & evidence

ORD record
ord-249b176810ef4aadbc47024b18b1e628
Source dataset
uspto-grants-2006_08
Patent number
US07094774B2

Reaction notes

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