4-Methylanisole → HCID 67417700, compound

HRID 2035398Notes

Reaction equation

HRID 2035398 reaction equation
C(O[CH:5]1[C@@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@H:8]([O:19][C:20](=[O:22])[CH3:21])[CH:7]([CH2:23][O:24][C:25](=[O:27])[CH3:26])[O:6]1)(=O)C.[CH3:28][O:29][C:30]1[CH:35]=[CH:34][C:33]([CH3:36])=[CH:32][CH:31]=1.[Sn](Cl)(Cl)(Cl)Cl>ClCCl.FC(F)(F)C([O-])=O.[Ag+]>[C:20]([O:19][C@H:8]1[C@H:9]([O:15][C:16](=[O:18])[CH3:17])[C@H:10]([O:11][C:12](=[O:14])[CH3:13])[C@H:5]([C:31]2[CH:32]=[C:33]([CH3:36])[CH:34]=[CH:35][C:30]=2[O:29][CH3:28])[O:6][CH:7]1[CH2:23][O:24][C:25](=[O:27])[CH3:26])(=[O:22])[CH3:21]

Participants

6

Reactant 3

HCID 77314-MethylanisoleHCID 24287Tin tetrachlorideHCID 67417301HCID 67417301, compound

Product 1

HCID 67417700HCID 67417700, compoundYield 76%

Reagents, catalysts & solvents 2

HCID 76299Silver trifluoroacetateCatalystHCID 6344DichloromethaneSolvent

Procedure

To a mixture of (3S,4S,5R)-6-(acetoxymethyl)tetrahydro-2H-pyran-2,3,4,5-tetrayl tetraacetate (1.0 g, 2.56 mmol, mixture of 2-α and 2-β), 4-methoxytoluene (0.65 mL, 5.12 mmol) and silver trifluoroacetate (0.85 g, 3.84 mmol) in dichloromethane (5.0 mL) at room temperature was added a solution of tin(IV) chloride (7.7 mL, 1.0 M in dichloromethane) dropwise. The reaction solution was stirred under nitrogen for 4 hours and then it was quenched with aqueous sodium bicarbonate and extracted with ethyl acetate (3×). The combined organic extract was washed with brine, dried over sodium sulfate and concentrated in vacuo. The crude product was purified by flash column chromatography (eluent: hexanes/ethyl acetate) to give (3R,4R,5R,6S)-2-(acetoxymethyl)-6-(2-methoxy-5-methylphenyl)tetrahydro-2H-pyran-3,4,5-triyl triacetate (0.88 g, 76%) as a orange oil: 1H NMR (CDCl3, 500 MHz) δ 7.18 (d, J=2.0 Hz, 1H), 7.07-7.05 (m, 1H), 6.75 (d, J=8.5 Hz, 1H), 5.35 (t, J=9.5 Hz, 1H), 5.28 (t, J=9.0 Hz, 1H), 5.23 (t, J=9.5 Hz, 1H), 4.92 (d, J=9.5 Hz, 1H), 4.28 (dd, J=12.5, 5.0 Hz, 1H), 4.14 (dd, J=12.0, 2.5 Hz, 1H), 3.84 (ddd, J=10.0, 5.0, 2.5 Hz, 1H), 3.80 (s, 3H), 2.28 (s, 3H), 2.08 (s, 3H), 2.05 (s, 3H), 2.00 (s, 3H), 1.77 (s, 3H).

Workup

  1. customit was quenched with aqueous sodium bicarbonate
  2. extractionextracted with ethyl acetate (3×)
  3. extractionThe combined organic extract
  4. washwas washed with brine
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customThe crude product was purified by flash column chromatography (eluent: hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-c3a37f2fd17a4d95839632daf80bedde
Source dataset
uspto-grants-2013_11
Patent number
US08575114B2

Reaction notes

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