Chlorotrimethylsilane → HCID 58388188, compound

HRID 1879097Notes

Reaction equation

HRID 1879097 reaction equation
C[Li].[CH2:3]([C:10]1([C:20]#[CH:21])[CH2:19][CH2:18][C:13]2([O:17][CH2:16][CH2:15][O:14]2)[CH2:12][CH2:11]1)[C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][CH:5]=1.[CH3:22][Si:23](Cl)([CH3:25])[CH3:24]>C1COCC1>[CH2:3]([C:10]1([C:20]#[C:21][Si:23]([CH3:25])([CH3:24])[CH3:22])[CH2:19][CH2:18][C:13]2([O:14][CH2:15][CH2:16][O:17]2)[CH2:12][CH2:11]1)[C:4]1[CH:5]=[CH:6][CH:7]=[CH:8][CH:9]=1

Participants

5

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 58388208HCID 58388208, compoundHCID 178418348HCID 178418348, compound

Product 1

HCID 58388188HCID 58388188, compoundYield 89.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

Under nitrogen atmosphere and with stirring at 0° C., methyllithium (1.6 M in hexanes, 4.78 mL, 7.65 mmol, 9.2 eq) was added dropwise to a solution of 28 (212.6 mg, 0.829 mmol) in dry THF (9.56 mL). The ice bath was then removed and the mixture was stirred at room temperature for 25 minutes. To the mixture was added dropwise a solution of trimethylsilyl chloride (3.24 mL, 24.87 mmol, 30 eq) in dry THF (3.9 mL) and the resulting mixture was stirred at room temperature for 45 minutes. During this time the solution became opaque and pale yellow. The reaction was then quenched with water (15 mL) and the aqueous layer was extracted with methylene chloride/ethyl ether (1:2, 3×15 mL). The organic layers were combined and washed with saturated aqueous sodium bicarbonate solution (1×15 mL) and brine (1×15 mL), dried over magnesium sulfate, filtered, and concentrated in vacuo to give 29 (243.1 mg, 0.74 mmol, 89%) as pale yellow crystals. The product was used in the next reaction without further purification: 1H NMR (CDCl3) δ 7.32-7.30 (5H, m), 3.95 (4H, dd, J=2.5, 3.5 Hz), 2.72 (2H, s), 2.00-1.90, 1.71-1.50 (8H, m), 0.14 (9H, s); 13C NMR (CDCl3) δ 137.8, 130.9, 127.7, 126.5, 110.6, 109.1, 88.2, 64.5, 64.4, 48.2, 38.0, 35.2, 31.9, 0.36. MS (EI) m/z 328.1 [M+], 284.2, 237.2, 193.1, 99.1 (100%), 73.1, 59.0; HRMS (EI) calcd for C20H28O2Si 328.1859. found 328.1856.

Workup

  1. customThe ice bath was then removed
  2. stirringthe mixture was stirred at room temperature for 25 minutes
  3. stirringthe resulting mixture was stirred at room temperature for 45 minutes
  4. customThe reaction was then quenched with water (15 mL)
  5. extractionthe aqueous layer was extracted with methylene chloride/ethyl ether (1:2, 3×15 mL)
  6. washwashed with saturated aqueous sodium bicarbonate solution (1×15 mL) and brine (1×15 mL)
  7. dry with materialdried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-ae0aab13c3224b9baf64111dce9b5753
Source dataset
uspto-grants-2012_11
Patent number
US08314137B2

Reaction notes

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