HCID 11077853, compound → HCID 11782782, compound

HRID 577493Notes

Reaction equation

HRID 577493 reaction equation
[Cu]C#N.[CH:4]([Mg]Br)=[CH2:5].[C:8]([Si:12]([O:25][CH2:26][C@@H:27]1[CH2:29][O:28]1)([C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)([CH3:11])([CH3:10])[CH3:9]>>[Si:12]([O:25][CH2:26][C@@H:27]([OH:28])[CH2:29][CH:4]=[CH2:5])([C:8]([CH3:10])([CH3:11])[CH3:9])([C:19]1[CH:20]=[CH:21][CH:22]=[CH:23][CH:24]=1)[C:13]1[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=1

Participants

4

Reactant 3

HCID 11077853HCID 11077853, compoundHCID 178418507HCID 178418507, compoundHCID 178418546HCID 178418546, compound

Product 1

HCID 11782782HCID 11782782, compoundYield 62.2%

Procedure

Copper (I) cyanide (3.60 g, 40.2 mmol) was placed in a three-necked flask under nitrogen and dried by gentle heating with a heat gun under vacuum. It was then allowed to cool to room temperature under nitrogen. This process was repeated three times, and then anhydrous tetrahydrofuran (80 mL) was added. The resulting mixture was cooled to −78° C., and then vinyl magnesium bromide (1 M solution in tetrahydrofuran, 88.5 mL, 88.5 mmol) was added dropwise while maintaining the internal temperature below −68° C. The heterogeneous mixture was warmed to −20° C. and stirred at this temperature for 30 minutes. After cooling the solution back to −78° C., tert-butyl[(2S)-oxiran-2-ylmethoxy]diphenylsilane (296 h, 8.38 g, 26.8 mmol) was added dropwise. The mixture was stirred, and allowed to gradually warm to room temperature, overnight. The reaction mixture was quenched with 100 mL ammonium hydroxide/ammonium chloride (1/10 2M NH4Cl), and extracted with ethyl acetate (200 mL). The organic layer was washed with brine (200 mL), dried over sodium sulfate, concentrated to dryness, and purified by silica gel chromatography (eluting with a gradient of 0-20% ethyl acetate in heptane), to give (2S)-1-{[tert-butyl(diphenyl)silyl]oxy}pent-4-en-2-ol (296i, 5.68 g, 62% yield) as a clear oil. 1H NMR (400 MHz, CDCl3) δ 7.65-7.71 (m, 4H), 7.36-7.49 (m, 6H), 5.75-5.87 (m, 1H), 5.03-5.14 (m, 2H), 3.76-3.85 (m, 1H), 3.66-3.72 (m, 1H), 3.54-3.61 (m, 1H), 2.45 (d, J=4.03 Hz, 1H), 2.23-2.30 (m, 2H), 1.09 (s, 9H). MS: 358 [M+18].

Workup

  1. customdried
  2. temperatureby gentle heating with a heat gun under vacuum
  3. additionanhydrous tetrahydrofuran (80 mL) was added
  4. temperatureThe resulting mixture was cooled to −78° C.
  5. temperaturewhile maintaining the internal temperature below −68° C
  6. temperatureThe heterogeneous mixture was warmed to −20° C.
  7. temperatureAfter cooling the solution back to −78° C.
  8. stirringThe mixture was stirred
  9. temperatureto gradually warm to room temperature, overnight
  10. customThe reaction mixture was quenched with 100 mL ammonium hydroxide/ammonium chloride (1/10 2M NH4Cl)
  11. extractionextracted with ethyl acetate (200 mL)
  12. washThe organic layer was washed with brine (200 mL)
  13. dry with materialdried over sodium sulfate
  14. concentrationconcentrated to dryness
  15. custompurified by silica gel chromatography (
  16. washeluting with a gradient of 0-20% ethyl acetate in heptane),

Sources & evidence

ORD record
ord-eb84f4eac7024b6db47a61cfe264cd15
Source dataset
uspto-grants-2015_05
Patent number
US09040515B2

Reaction notes

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