Hepta-1,6-dien-4-ol → HCID 25137413, compound

HRID 1889133Notes

Reaction equation

HRID 1889133 reaction equation
[H-].[Na+].[CH2:3]=[CH:4][CH2:5][CH:6]([OH:10])[CH2:7][CH:8]=[CH2:9].[C:11]([Si:15]([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)Cl)([CH3:14])([CH3:13])[CH3:12]>C1COCC1>[Si:15]([O:10][CH:6]([CH2:7][CH:8]=[CH2:9])[CH2:5][CH:4]=[CH2:3])([C:11]([CH3:14])([CH3:13])[CH3:12])([C:23]1[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=1)[C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1

Participants

5

Reactant 3

HCID 17902Hepta-1,6-dien-4-olHCID 24758Sodium hydrideHCID 94078tert-Butyldiphenylchlorosilane

Product 1

HCID 25137413HCID 25137413, compoundYield 96.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a suspension of sodium hydride (60% in mineral oil, 0.92 g, 23 mmol) in THF (10 mL), cooled to 0° C., 1,6-heptadien-4-ol 104 (1 mL, 7.7 mmol) was added dropwise in 10 sec. The resulting suspension was stirred at 0° C. for 30 min and then tert-butyldiphenylchlorosilane (2 mL, 7.9 mmol) was added. The reaction mixture was stirred at 23° C. for 4 h and then quenched with a saturated solution of ammonium chloride. The solvent was removed in vacuo and the aqueous phase was extracted with CH2Cl2. The organic extracts were dried (Na2SO4), the solvent was removed and the residue was purified by flash-chromatography (1:10 EtOAc/Hex) to afford 30 4-(tert-butyldiphenylsilyloxy)hepta-1,6-diene (2.6 g, 96%) as a colorless oil: δH (300 MHz, CDCl3) 7.70 (4H, dd, J1.6, 7.6 Hz, ArH), 7.47-7.38 (6H, m, ArH), 5.83-5.69 (2H, m, 2 CH═CH2), 5.02-4.91 (4H, m, 2.CH═CH2), 3.87-3.80 (1H, m, CHOSi), 2.31-2.12 (4H, m, 3-H2, 5-H2) and 1.08 [9H, s, 35 C(CH3)3]. To a solution of the above compound (2.0 g, 5.7 mmol) in dry CH2Cl2 (20 mL), second generation Grubbs catalyst (4.8 mg, 5.6 μmol) was added and the resulting mixture was heated under reflux for 2 h. Subsequently, the reaction mixture was cooled to 23° C., the solvent was 40 removed under reduced pressure and the residue was purified by flash-chromatography (1:10 EtOAc/Hex) to afford 105 (1.8 g, 98%) as a colorless oil: δH (300 MHz, CDCl3) 7.67 (4H, dd, J1.8, 7.8, ArH), 7.45-7.34 (6H, m, ArH), 5.61 (2 H, s, 1-H, 2-H), 4.57-4.51 (1H, m, 4-H), 2.47-2.33 (4H, m, 3-H2, 5-H2) 45 and 1.05 [9H, s, C(CH3)3].

Workup

  1. stirringThe reaction mixture was stirred at 23° C. for 4 h
  2. customquenched with a saturated solution of ammonium chloride
  3. customThe solvent was removed in vacuo
  4. extractionthe aqueous phase was extracted with CH2Cl2
  5. dry with materialThe organic extracts were dried (Na2SO4)
  6. customthe solvent was removed
  7. customthe residue was purified by flash-chromatography (1:10 EtOAc/Hex)

Sources & evidence

ORD record
ord-133e1a58da73432198fc573a72f2336b
Source dataset
uspto-grants-2013_08
Patent number
US08501961B2

Reaction notes

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