(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 1937072Notes

Reaction equation

HRID 1937072 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-5d2ed43e8ec44d358e3659b8ae24cced
Source dataset
uspto-grants-2002_05
Patent number
US06392071B1

Reaction notes

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