Hydrochloric Acid → HCID 71270633, compound

HRID 2406273Notes

Reaction equation

HRID 2406273 reaction equation
[CH2:1]([O:8][C@H:9]1[CH2:13][C@@H:12]([O:14][Si](C)(C)C)[CH:11]=[C:10]1[CH2:19][O:20][CH2:21][C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[H][H].Cl>O1CCCC1.[Pd].C(OCC)(=O)C.O>[CH2:1]([O:8][C@@H:9]1[C@H:10]([CH2:19][O:20][CH2:21][C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[CH2:11][C@H:12]([OH:14])[CH2:13]1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

8

Reactant 3

HCID 313Hydrochloric AcidHCID 71270603HCID 71270603, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 71270633HCID 71270633, compoundYield 88.1%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolventHCID 23938PalladiumSolvent

Procedure

To a solution of ((1R,4S)-4-(benzyloxy)-3-(benzyloxymethyl)cyclopent-2-enyloxy)trimethylsilane (22) (478.00 g, 1.2494 mol) in tetrahydrofuran (9.6 L), Pd, 5 wt % on barium sulfate (265.9 g, 0.1249 mol) was added and the mixture was stirred under 100 psi of hydrogen at ambient temperature for 18 hours, stirring at 200 rpm. HPLC analysis after 18 hours indicated consumption of starting material. The reaction mixture was filtered through a medium frit funnel and the bed was washed with tetrahydrofuran (2000 mL). The filtrate was concentrated, yielding a yellow oil. The resulting oil was taken up in ethyl acetate (2000 mL) to which 2.0 M of hydrochloric acid in water (2000 mL) was added, and the biphasic mixture was stirred for 1 hour. The organic layer was separated and extracted once with saturated sodium bicarbonate in water (2000 mL), twice with 2.0 M of sodium hydroxide in water (2000 mL) and finally with saturated sodium chloride in water (2000 mL). The organic layer was concentrated to give a brown oil (344 g, 88%) which was used without further purification. 1H NMR (300 MHz, CD3OD, δ): 7.18 (m, 10H), 4.38 (m, 4H), 4.12 (m, 1H), 3.85 (t, 1H), 3.68 (m, 1H), 3.44 (m, 1H), 2.00 (m, 3H), 1.75 (m, 1H) and 1.42 (m, 1H).

Workup

  1. customconsumption of starting material
  2. filtrationThe reaction mixture was filtered through a medium frit funnel
  3. washthe bed was washed with tetrahydrofuran (2000 mL)
  4. concentrationThe filtrate was concentrated
  5. customyielding a yellow oil
  6. additionwas added
  7. stirringthe biphasic mixture was stirred for 1 hour
  8. customThe organic layer was separated
  9. extractionextracted once with saturated sodium bicarbonate in water (2000 mL), twice with 2.0 M of sodium hydroxide in water (2000 mL) and finally with saturated sodium chloride in water (2000 mL)
  10. concentrationThe organic layer was concentrated

Sources & evidence

ORD record
ord-8f863badf00f4678aa0f4ddc8026743b
Source dataset
uspto-grants-2014_08
Patent number
US08809356B2

Reaction notes

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