HCID 9799634, compound → HCID 9886493, compound

HRID 840734Notes

Reaction equation

HRID 840734 reaction equation
[C:1]1([CH2:7][O:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=2[C:15]2[CH:19]=[CH:18][S:17][C:16]=2[C:20]2[CH:25]=[CH:24][C:23]([CH2:26][OH:27])=[CH:22][CH:21]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH3:28][Mg+].[Br-]>C(Cl)Cl.CCOCC.O=[Mn]=O>[C:1]1([CH2:7][O:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=2[C:15]2[CH:19]=[CH:18][S:17][C:16]=2[C:20]2[CH:21]=[CH:22][C:23]([CH:26]([OH:27])[CH3:28])=[CH:24][CH:25]=2)[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

6

Reactant 2

HCID 9799634HCID 9799634, compoundHCID 178418689HCID 178418689, compound

Product 1

HCID 9886493HCID 9886493, compound

Reagents, catalysts & solvents 3

HCID 14801Manganese dioxideCatalystHCID 3283Diethyl EtherSolvent2×HCID 6344DichloromethaneSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of the alcohol of example 4 (200 mg, 0.536 mmol) in CH2Cl2 is added MnO2 (467 mg, 5.36 mmol) and the mixture is stirred overnight. The reaction is then filtred throught a plug of celite and the crude mixture diluted in ether (5.0 mL) and cooled at −78° C. MeMgBr was then added (3M in ether, 0.22 mL, 0.66 mmol) and the reaction was warmed to room temperature and stirred for 1 h. The mixture was quenched with saturated NH4Cl, diluted with Et2O and washed successively with HCl 10%, aq. NaHCO3 and brine. The ether layer was dried with anh. MgSO4, filtered and concentrated under reduced pressure to give a residue which was separated in two and one part was purified by flash chromatography (70% Hexanes/30% AcOEt) to provide the title compound (19.4 mg). 1H nmr (400 MHz, acetone-d6) δ ppm 7.45 (1H, d, J=7.5 Hz), 7.32-7.05 (13H, m), 6.91 (1H, t, J=7.5 Hz), 4.97 (2H, s), 4.80 (1H, m) 4.12 (1H, d, J=5.0 Hz), 3.95 (3H, d, J=7.5 Hz).

Workup

  1. temperaturethe reaction was warmed to room temperature
  2. stirringstirred for 1 h
  3. customThe mixture was quenched with saturated NH4Cl
  4. additiondiluted with Et2O
  5. washwashed successively with HCl 10%, aq. NaHCO3 and brine
  6. dry with materialThe ether layer was dried with anh. MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customto give a residue which
  10. customwas separated in two and one part
  11. customwas purified by flash chromatography (70% Hexanes/30% AcOEt)

Sources & evidence

ORD record
ord-84fcd99d452d469286c39a11454775e5
Source dataset
uspto-grants-2002_04
Patent number
US06369084B1

Reaction notes

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