Sodium hydride → Methyl 8-t-butyldimethylsilyloxy-8-(2-naphthyl)-2-octenoate

HRID 1182504Notes

Reaction equation

HRID 1182504 reaction equation
[H-].[Na+].C(OP([CH2:11][C:12]([O:14][CH3:15])=[O:13])(OCC)=O)C.[Si:16]([O:23][CH:24]([C:31]1[CH:40]=[CH:39][C:38]2[C:33](=[CH:34][CH:35]=[CH:36][CH:37]=2)[CH:32]=1)[CH2:25][CH2:26][CH2:27][CH2:28][CH:29]=O)([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17]>C1COCC1>[Si:16]([O:23][CH:24]([C:31]1[CH:40]=[CH:39][C:38]2[C:33](=[CH:34][CH:35]=[CH:36][CH:37]=2)[CH:32]=1)[CH2:25][CH2:26][CH2:27][CH2:28][CH:29]=[CH:11][C:12]([O:14][CH3:15])=[O:13])([C:19]([CH3:20])([CH3:21])[CH3:22])([CH3:18])[CH3:17]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 66113Methyl diethylphosphonoacetateHCID 109482766-t-Butyldimethylsilyloxy-6-(2-naphthyl)hexanal

Product 1

HCID 68620757Methyl 8-t-butyldimethylsilyloxy-8-(2-naphthyl)-2-octenoateYield 63%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

To a suspension of sodium hydride (60% in mineral oil, 177 mg, 4.42 mmol) in THF (25 mL) at room temperature under nitrogen atmosphere was added dropwise neat methyl diethylphosphonoacetate (811 μL, 4.42 mmol). The resulting solution was stirred for 10 minutes while cooling down to 0° C. A solution of crude aldehyde 183 (1.05 g, 2.94 mmol) in THF (10 mL) was transferred via cannula. The resulting solution was stirred for 15 minutes at 0° C. and quenched with a saturated aqueous solution of ammonium chloride. The THF was evaporated in vacuo and the aqueous residue was partitioned between diethyl ether and water. The aqueous layer was extracted with diethyl ether and the combined organic layers were washed with brine, dried (MgSO4) and concentrated in vacuo. The crude residue was purified by flash chromatography (5% ethyl acetate/hexane), affording the title compound 184 in 63% yield (1.30 g). 1H NMR: (300 MHz, CDCl3) δ: 7.83-7.78 (m, 3H), 7.69 (s, 1H), 7.49-7.41 (m, 3H), 6.94 (dt, J=15.4, 7.1 Hz, 1H), 5.79 (dt, J=15.7, 1.1 Hz, 1H), 4.79 (dd, J=7.1, 5.2 Hz, 1H), 3.71 (s, 3H), 2.16 (q, J=7.4 Hz, 2H), 1.81-1.62 (m, 2H), 1.48-1.29 (m, 4H), 0.90 (s, 9H), 0.04 (s, 3H), −0.15 (s, 3H). MS (ESI)=413 (MH+).

Workup

  1. stirringThe resulting solution was stirred for 15 minutes at 0° C.
  2. customquenched with a saturated aqueous solution of ammonium chloride
  3. customThe THF was evaporated in vacuo
  4. customthe aqueous residue was partitioned between diethyl ether and water
  5. extractionThe aqueous layer was extracted with diethyl ether
  6. washthe combined organic layers were washed with brine
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated in vacuo
  9. customThe crude residue was purified by flash chromatography (5% ethyl acetate/hexane)

Sources & evidence

ORD record
ord-5a4104ce2daf48c7a6b8d698d2a95ba9
Source dataset
uspto-grants-2007_10
Patent number
US07288567B2

Reaction notes

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