Chlorosuccinimide → HCID 87190441, compound

HRID 2204046Notes

Reaction equation

HRID 2204046 reaction equation
[C:1]([O:4][C@@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:9]([C:15]2[CH:20]=[CH:19][C:18]([Cl:21])=[C:17]([CH2:22][C:23]3[CH:28]=[CH:27][C:26]([O:29][CH2:30][CH3:31])=[CH:25][CH:24]=3)[CH:16]=2)[O:8][CH:7](O)[C@H:6]1[O:33][C:34](=[O:36])[CH3:35])(=[O:3])[CH3:2].Cl.[NH2:38][OH:39].C1CCN2C(=NCCC2)CC1.ClN1C(=O)CCC1=O>N1C=CC=CC=1.CCOC(C)=O>[C:1]([O:4][C@@H:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:9]([C:15]2[CH:20]=[CH:19][C:18]([Cl:21])=[C:17]([CH2:22][C:23]3[CH:28]=[CH:27][C:26]([O:29][CH2:30][CH3:31])=[CH:25][CH:24]=3)[CH:16]=2)[O:8]/[C:7](=[N:38]\[OH:39])/[C@H:6]1[O:33][C:34](=[O:36])[CH3:35])(=[O:3])[CH3:2]

Participants

7

Reactant 4

HCID 31398ChlorosuccinimideHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 443297Hydroxyamine hydrochlorideHCID 66885752HCID 66885752, compound

Product 1

HCID 87190441HCID 87190441, compoundYield 67%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 8857Ethyl AcetateSolvent2×

Conditions

Temperature
-78 °C

Procedure

Compound from step A (142 mg, 0.27 mmol) and hydroxylamine hydrochloride (57 mg, 0.82 mmol) were dissolved in pyridine (1.4 ml). The reaction was stirred for 6 hours, diluted with EtOAc, washed with 1 M aq. NaHSO4, H2O, sat. aq. NaHCO3, and brine (with back extraction), dried over Na2SO4, filtered, and concentrated under vacuum. The residue was dissolved in CH2Cl2, cooled to −78° C., and treated with DBU (49 μL, 0.33 mmol) followed by N-chlorosuccinimide (44 mg, 0.33 mmol). The reaction was stirred for 20 minutes at −78° C., then allowed to warm to room temperature over 15 minutes The reaction was diluted with EtOAc, washed with H2O and brine (with back extraction), dried over MgSO4, filtered, and concentrated under vacuum. The residue was purified by flash chromatography (12 g SiO2, 0-50% EtOAc:Hex.) to give acetic acid (3S,4R,5S,6S)-4,5-diacetoxy-6-[4-chloro-3-(4-ethoxy-benzyl)-phenyl]-2-[(Z)-hydroxyimino]-tetrahydro-pyran-3-yl ester (97 mg, 0.18 mmol, 67%).

Workup

  1. washwashed with 1 M aq. NaHSO4, H2O, sat. aq. NaHCO3, and brine (with back extraction)
  2. dry with materialdried over Na2SO4
  3. filtrationfiltered
  4. concentrationconcentrated under vacuum
  5. dissolutionThe residue was dissolved in CH2Cl2
  6. stirringThe reaction was stirred for 20 minutes at −78° C.
  7. temperatureto warm to room temperature over 15 minutes The reaction
  8. washwashed with H2O and brine (with back extraction)
  9. dry with materialdried over MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated under vacuum
  12. customThe residue was purified by flash chromatography (12 g SiO2, 0-50% EtOAc:Hex.)

Sources & evidence

ORD record
ord-5ba4c81ab9704e56aedfb3b4653c39ff
Source dataset
uspto-grants-2016_06
Patent number
US09365602B2

Reaction notes

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