Methanol → (7S)-2,9,9-Trimethoxy-7beta-methyl-7,8,9,10-tetrahydrophenanthridine-6,10alpha-diol 6-(trifluoromethanesulfonate)

HRID 1457795Notes

Reaction equation

HRID 1457795 reaction equation
[F:1][C:2]([F:27])([F:26])[S:3]([O:6][C:7]1[N:8]=[C:9]2[C:14](=[C:15]3[C:20]=1[C@@H:19]([CH3:21])[CH2:18][C:17]([O:22][CH3:23])=[CH:16]3)[CH:13]=[C:12]([O:24][CH3:25])[CH:11]=[CH:10]2)(=[O:5])=[O:4].C1C=C(Cl)C=C([C:35](OO)=[O:36])C=1.C[OH:40]>>[F:27][C:2]([F:1])([F:26])[S:3]([O:6][C:7]1[N:8]=[C:9]2[C:14](=[C:15]3[C:20]=1[C@@H:19]([CH3:21])[CH2:18][C:17]([O:36][CH3:35])([O:22][CH3:23])[C@@H:16]3[OH:40])[CH:13]=[C:12]([O:24][CH3:25])[CH:11]=[CH:10]2)(=[O:5])=[O:4]

Participants

4

Reactant 3

HCID 887MethanolHCID 70297m-Chloroperbenzoic acidHCID 18660709(S)-7,8-dihydro-2,9-dimethoxy-7-methyl-6-phenanthridinol trifluoromethanesulfonate

Product 1

HCID 57051562(7S)-2,9,9-Trimethoxy-7beta-methyl-7,8,9,10-tetrahydrophenanthridine-6,10alpha-diol 6-(trifluoromethanesulfonate)Yield 63%

Conditions

Temperature
23 °C

Procedure

A solution of (S)-7,8-dihydro-2,9-dimethoxy-7-methyl-6-phenanthridinol trifluoromethanesulfonate (ester) (12, 3.00 g, 7.40 mmol, 1 equiv) and m-CPBA (5.10 g, 14.9 mmol, 2.00 equiv) in methanol (120 mL) was heated at reflux for 1 h. After cooling to 23° C., the reaction solution was partitioned between 1:1 saturated aqueous sodium bicarbonate solution:saturated aqueous sodium thiosulfate solution (200 mL) and dichloromethane (200 mL). The aqueous layer was separated and extracted further with dichloromethane (2×200 mL). The combined organic layers were dried over sodium sulfate and were concentrated. The residue was purified by flash column chromatography (25% ethyl acetate-hexanes initially, grading to 40% ethyl acetate-hexanes) away from structure 14 to afford (7S, 10R)-7,8,9,10-tetrahydro-2,9,9-trimethoxy-7-methyl-6,10-phenanthridinediol 6-(trifluoro-methanesulfonate) (13) as a yellow foam (2.12 g, 63%).

Workup

  1. temperatureat reflux for 1 h
  2. customthe reaction solution was partitioned between 1:1 saturated aqueous sodium bicarbonate solution
  3. customThe aqueous layer was separated
  4. extractionextracted further with dichloromethane (2×200 mL)
  5. dry with materialThe combined organic layers were dried over sodium sulfate
  6. concentrationwere concentrated
  7. customThe residue was purified by flash column chromatography (25% ethyl acetate-hexanes initially

Sources & evidence

ORD record
ord-97ee9663af1a4daeb3c319d96934150a
Source dataset
uspto-grants-1998_12
Patent number
US05849750

Reaction notes

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