Water → HCID 131728084, compound

HRID 645453Notes

Reaction equation

HRID 645453 reaction equation
[H-].[Na+].C([C:5]([CH2:14][CH3:15])(P(=O)([O-])[O-])[C:6]([O:8][CH3:9])=[O:7])C.[C:16]([SiH2:20][O:21][C:22]([C:39]1[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=1)([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)[CH:23]1[CH2:27][CH2:26][C:25](C)(C=O)[C:24]1(C)[CH3:31])([CH3:19])([CH3:18])[CH3:17].O.[CH2:46]1COCC1>>[CH3:9][O:8][C:6](=[O:7])[CH:5]=[CH:14][C:15]1([CH3:46])[CH2:26][CH2:27][CH:23]([C:22]([C:33]2[CH:34]=[CH:35][CH:36]=[CH:37][CH:38]=2)([C:39]2[CH:40]=[CH:41][CH:42]=[CH:43][CH:44]=2)[O:21][SiH2:20][C:16]([CH3:18])([CH3:19])[CH3:17])[C:24]1([CH3:25])[CH3:31]

Participants

6

Reactant 5

HCID 962WaterHCID 8028Tetrahydrofuran2×HCID 24758Sodium hydrideHCID 131728082HCID 131728082, compoundHCID 131728085HCID 131728085, compound

Product 1

HCID 131728084HCID 131728084, compoundYield 98%

Conditions

Temperature
0 °C

Procedure

To a suspension of NaH (60% dispersion in petroleum ether; 1.47 g, 36.7 mmole) in dry THF (50 mL) at 0° C. was added dropwise diethylmethoxy-carbonylmethylphosphonate (6.88 mL, 36.71 mmole) over a period of 10 minutes. The solution was stirred at 0° C. for 35 minutes (color change to pale yellow) and 3-(tert-butyldiphenylsilanyloxymethyl)-1,2,2-trimethyl-cyclo-pentanecarbaldehyde (4) (10.0 g, 24.47 mmole) in dry THF (20 mL) was added dropwise over a period of 20 minutes. The reaction mixture was stirred at 0° C. for 3 hours and poured into cold water (500 mL). The aqueous layer was extracted with Et2O (4×100 mL) and the combined organic layers were dried over anhydrous MgSO4. The solvent was removed in vacuo and the residue was purified over a short column of silica (n-hexane/ethyl acetate, 9:1) and further purified over silica (n-hexane/ethyl acetate, 95:5) to afford 11.15 g (98% yield) of the desired intermediate (5) as a colorless oil which was characterized as follows:

Workup

  1. additionwas added dropwise over a period of 20 minutes
  2. extractionThe aqueous layer was extracted with Et2O (4×100 mL)
  3. dry with materialthe combined organic layers were dried over anhydrous MgSO4
  4. customThe solvent was removed in vacuo
  5. customthe residue was purified over a short column of silica (n-hexane/ethyl acetate, 9:1)
  6. customfurther purified over silica (n-hexane/ethyl acetate, 95:5)

Sources & evidence

ORD record
ord-5f3efc71df4d47eaa914a1d0d7e885e4
Source dataset
uspto-grants-2010_04
Patent number
US07704986B2

Reaction notes

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