Water → HCID 86686473, compound

HRID 513254Notes

Reaction equation

HRID 513254 reaction equation
O[C:2]1[C:3]2[C:8]([C:9]([O:27][CH3:28])=[C:10]3[C:15]=1[C:14](=[O:16])[CH2:13][CH2:12][C@@H:11]3[O:17][CH2:18][C:19]1[CH:24]=[CH:23][C:22]([O:25][CH3:26])=[CH:21][CH:20]=1)=[CH:7][C:6]([CH3:29])=[C:5](/[CH:30]=C/C)[C:4]=2[O:33][CH2:34][O:35][CH3:36].N1C(C)=CC=CC=1C.I([O-])(=O)(=O)=[O:46].[Na+].[OH2:51]>O1CCCC1>[OH:51][C:2]1[C:15]2[C:14](=[O:16])[CH2:13][CH2:12][C@H:11]([O:17][CH2:18][C:19]3[CH:24]=[CH:23][C:22]([O:25][CH3:26])=[CH:21][CH:20]=3)[C:10]=2[C:9]([O:27][CH3:28])=[C:8]2[C:3]=1[C:4]([O:33][CH2:34][O:35][CH3:36])=[C:5]([CH:30]=[O:46])[C:6]([CH3:29])=[CH:7]2

Participants

6

Reactant 4

HCID 962WaterHCID 79372,6-LutidineHCID 23667635Sodium periodateHCID 86686474HCID 86686474, compound

Product 1

HCID 86686473HCID 86686473, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
23 °C

Procedure

Potassium osmate dihydrate (29 mg, 0.079 mmol, 0.05 equiv) was added to an ice-cooled mixture of (S,E)-9-hydroxy-10-methoxy-4-(4-methoxybenzyloxy)-8-(methoxymethoxy)-6-methyl-7-(prop-1-enyl)-3,4-dihydroanthracen-1-one (780 mg, 1.58 mmol, 1 equiv), 2,6-lutidine (369 μL, 3.17 mmol, 2.0 equiv), and sodium periodate (1.36 g, 6.33 mmol, 4.0 equiv) in a mixture of tetrahydrofuran (20 mL) and water (10 mL). After 10 min, the cooling bath was removed and the reaction flask was allowed to warm to 23° C. After 1.5 h, the reaction mixture was partitioned between water (100 mL) and ethyl acetate (150 mL). The layers were separated. The organic layer was washed with aqueous sodium chloride solution (50 mL) and the washed solution was dried over sodium sulfate. The dried solution was filtered and the filtrate was concentrated. The residue was purified by flash-column chromatography (20% ethyl acetate-hexanes) to provide 498 mg of the product, (S)-9-hydroxy-10-methoxy-5-(4-methoxybenzyloxy)-1-(methoxymethoxy)-3-methyl-8-oxo-5,6,7,8-tetrahydroanthracene-2-carbaldehyde, as an orange foam (65%). 1H NMR (500 MHz, CDCl3): 15.17 (s, 1H), 10.74 (s, 1H), 7.66 (s, 1H), 7.27 (d, 2H, J=8.5 Hz), 6.86 (d, 2H, J=8.6 Hz), 5,30-5.18 (m, 3H), 4.63 (d, 1H, J=11.1 Hz), 4.52 (d, 1H, J=12.0 Hz), 3.86 (s, 3H), 3.79 (s, 3H), 3.62 (s, 3H), 3.22 (m, 1H), 2.75 (s, 3H), 2.63 (m, 1H), 2.54 (m, 1H), 2.08 (m, 1H). 13C NMR (125 MHz, CDCl3): 204.9, 193.2, 163.2, 161.7, 159.2, 144.4, 141.7, 137.0, 130.1, 129.4, 120.7, 117.9, 113.8, 110.0, 102.8, 70.4, 67.2, 62.9, 58.3, 55.2, 32.3, 26.3, 22.2. FTIR, cm−1 (thin film): 2936 (m), 2907 (m), 1684 (s), 1611 (s), 1377 (s), 1246 (s). HRMS (ESI): Calcd for (C27H28O8+K)+:519.1416; Found 519.1368. TLC (20% ethyl acetate-hexanes): Rf=0.17 (CAM)

Workup

  1. temperaturecooled
  2. customthe cooling bath was removed
  3. waitAfter 1.5 h
  4. customthe reaction mixture was partitioned between water (100 mL) and ethyl acetate (150 mL)
  5. customThe layers were separated
  6. washThe organic layer was washed with aqueous sodium chloride solution (50 mL)
  7. dry with materialthe washed solution was dried over sodium sulfate
  8. filtrationThe dried solution was filtered
  9. concentrationthe filtrate was concentrated
  10. customThe residue was purified by flash-column chromatography (20% ethyl acetate-hexanes)

Sources & evidence

ORD record
ord-f513af3ab2794d6589fd76be24c2bfc3
Source dataset
uspto-grants-2015_08
Patent number
US09102697B2

Reaction notes

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