Hydrochloric Acid → HCID 117986083, compound

HRID 1055620Notes

Reaction equation

HRID 1055620 reaction equation
C([O:8][C@@H:9]1[C@@H:15]([O:16]CC2C=CC=CC=2)[C@:14]2([C:25]3[CH:30]=[CH:29][C:28]([Cl:31])=[C:27]([CH2:32][C:33]4[CH:38]=[CH:37][C:36]([O:39][CH2:40][CH3:41])=[CH:35][CH:34]=4)[CH:26]=3)[O:24][C@@:11]([CH:42]([OH:44])[CH3:43])([CH2:12][O:13]2)[C@@H:10]1[OH:45])C1C=CC=CC=1.Cl>[Pd].CO.O1CCCC1>[Cl:31][C:28]1[CH:29]=[CH:30][C:25]([C@@:14]23[O:24][C@@:11]([CH:42]([OH:44])[CH3:43])([CH2:12][O:13]2)[C@H:10]([OH:45])[C@H:9]([OH:8])[C@H:15]3[OH:16])=[CH:26][C:27]=1[CH2:32][C:33]1[CH:34]=[CH:35][C:36]([O:39][CH2:40][CH3:41])=[CH:37][CH:38]=1

Participants

5

Reactant 2

HCID 313Hydrochloric AcidHCID 118377791HCID 118377791, compound

Product 1

HCID 117986083HCID 117986083, compoundYield 14.1%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 21899815MeOH tetrahydrofuranSolvent

Procedure

To a solution of (1R,2R,3S,4R,5S)-3,4-dibenzyloxy-5-[4-chloro-3-[(4-ethoxyphenyl)methyl]phenyl]-1-(1-hydroxyethyl)-6,8-dioxabicyclo[3.2.1]octan-2-ol 281 (140 mg, 0.22 mmol) in a methanol/tetrahydrofuran mixture (v/v=4/1, 20 mL) were added hydrochloric acid (0.03 mL, 1.1 lmmol) and Pd/C (23 mg, 0.02 mmol, 10%) at room temperature. The mixture was stirred at room temperature under H2 for 1 hour and filtered. The filtrate was adjusted with saturated aqueous sodium bicarbonate till pH becomes 7 and extracted with ethyl acetate (10 mL×3). The combined organic layers were washed with water (10 mL×3) and saturated aqueous sodium chloride (10 mL×2), dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated in vacuo. The residue was purified by silica gel chromatography eluted with EtOAc to give the title compound 28 as a white solid (14 mg, 14.1%, HPLC: 86.0%). The compound was characterized by the following spectroscopic data: 1H NMR (600 MHz, DMSO-d6) δ(ppm): 7.45 (s, 1H), 7.40 (m, 1H), 7.34 (m, 1H), 7.10 (d, 2H), 6.83 (d, 2H), 5.35-5.30 (m, 1H), 4.78 (d, 1H), 4.68 (s, 2H), 4.60 (d, 1H), 4.21-4.16 (m, 1H), 4.02-3.95 (m, 4H), 3.82-3.75 (m, 1H), 3.71 (d, 1H), 3.66-3.55 (m, 2H), 1.30 (t, 3H), 1.02 (d, 3H); and MS (ESI, pos. ion) m/z: 451.1[M+H]+.

Workup

  1. filtrationfiltered
  2. extractionextracted with ethyl acetate (10 mL×3)
  3. washThe combined organic layers were washed with water (10 mL×3) and saturated aqueous sodium chloride (10 mL×2)
  4. dry with materialdried over anhydrous sodium sulfate
  5. filtrationfiltered
  6. concentrationThe filtrate was concentrated in vacuo
  7. customThe residue was purified by silica gel chromatography
  8. washeluted with EtOAc

Sources & evidence

ORD record
ord-7347503ebf014c748f113fb7d700f513
Source dataset
uspto-grants-2016_07
Patent number
US09394329B2

Reaction notes

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