Sodium Hydroxide → HCID 86741642, compound

HRID 653334Notes

Reaction equation

HRID 653334 reaction equation
[C:1]([O:4][C@@H:5]1[C@@H:14]([O:15][C:16](=[O:18])[CH3:17])[C@H:13]([O:19][C@@H:20]2[O:57][C@H:56]([CH2:58][O:59][C:60](=[O:62])[CH3:61])[C@H:31]([O:32][C@H:33]3[O:50][C@H:49]([CH2:51][O:52][C:53](=[O:55])[CH3:54])[C@H:44]([O:45][C:46](=[O:48])[CH3:47])[C@H:39]([O:40][C:41](=[O:43])[CH3:42])[C@H:34]3[O:35][C:36](=[O:38])[CH3:37])[C@H:26]([O:27][C:28](=[O:30])[CH3:29])[C@H:21]2[O:22][C:23](=[O:25])[CH3:24])[C@@H:12]([CH2:63][O:64][C:65](=[O:67])[CH3:66])[O:11][C@H:6]1[O:7][CH2:8][CH2:9]Br)(=[O:3])[CH3:2].[OH-].[Na+]>C[O-].[Na+].O.[Pd]>[C:1]([O:4][C@@H:5]1[C@@H:14]([O:15][C:16](=[O:18])[CH3:17])[C@H:13]([O:19][C@@H:20]2[O:57][C@H:56]([CH2:58][O:59][C:60](=[O:62])[CH3:61])[C@H:31]([O:32][C@H:33]3[O:50][C@H:49]([CH2:51][O:52][C:53](=[O:55])[CH3:54])[C@H:44]([O:45][C:46](=[O:48])[CH3:47])[C@H:39]([O:40][C:41](=[O:43])[CH3:42])[C@H:34]3[O:35][C:36](=[O:38])[CH3:37])[C@H:26]([O:27][C:28](=[O:30])[CH3:29])[C@H:21]2[O:22][C:23](=[O:25])[CH3:24])[C@@H:12]([CH2:63][O:64][C:65](=[O:67])[CH3:66])[O:11][C@H:6]1[O:7][CH2:8][CH3:9])(=[O:3])[CH3:2]

Participants

6

Reactant 2

HCID 14798Sodium HydroxideHCID 88261924HCID 88261924, compound

Product 1

HCID 86741642HCID 86741642, compoundYield 63%

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 962WaterSolventHCID 10942334Sodium MethoxideSolvent

Procedure

A solution of 59 (0.52 g, 0.5 mmol) in methanolic sodium methoxide (0.007M, 40 ml) was left at room temperature for 2 h and sodium hydroxide (95 mg) in water (2 ml) was added. The mixture was hydrogenated (atm. pressure, Pd/C, 10%, 100 mg) for 100 min, filtered, neutralized with M hydrochloric acid and the solvent was removed. The residue was acetylated (acetic anhydride-pyridine 1:1, 100 ml) for 17 h at room temperature and then co-concentrated with toluene. The residue wa partitioned between dichloromethane (100 ml) and water (25 ml) and the organic phase was dried (Na2SO4) and concentrated. Column (5×18 cm) chromatography (SiO2, ethyl acetate:isooctane 2:1) gave amorphous 67 (300 mg, 62%) with [α]D21 +41° (c 1.0 chloroform). 1H-NMR (CDCl3, Me4Si) δ 5.91 (d, 1H, J=3 Hz, H4"), 5.40 (dd, 1H, J=11 and 3 Hz, H3"), 5.21 (t, 1H, J=9 Hz, H3), 5.18 (dd, 1H, J=11 and 3.5 Hz, H2"), 5.11 (dd, 1H, J=11 and 8 Hz, H2'), 4.99 (d, 1H, J=3.5 Hz, H1"), 4.88 (dd, 1H, J=9 and 8 Hz, H2), 4.73 (dd, 1H, J=11 and 2.5 Hz, H3'), 4.56-4.38 (5H, inter alia H1 and H1'), 4.23-4.03 (4H), 4.02 (d, 1H, J=2.5 Hz, H4'), 3.98-3.70 (3H), 3.69-3.46 (2H), 2.14-1.98 (MeCO), 1.19 (t, 3H, J=7 Hz, CH3--CH2). 13C-NMR (CDCl3, Me4Si) δ 170.4, 170.3 (4C), 169.9, 169.6, 169.5, 169.4, 168.7, 100.9, 100.1 (2d, J=160 and 164 Hz, Cl, Cl'), 99.4 (d, J=172 Hz, Cl"), 76.8, 76.3, 73.0, 72.6, 72.3, 71.6, (2C), 68.8, 68.6, 67.7, 66.9, 66.9, 65.4 (CH2), 62.1 (CH2), 61.2 (CH2), 60.1 (CH2), 20.8, 20.7, 20.54 (3C), 20.5 (2C), 20.46, 20.4, 20.3, 14.9.

Workup

  1. customfor 100 min
  2. filtrationfiltered
  3. customthe solvent was removed
  4. customfor 17 h
  5. customat room temperature
  6. customThe residue wa partitioned between dichloromethane (100 ml) and water (25 ml)
  7. dry with materialthe organic phase was dried (Na2SO4)
  8. concentrationconcentrated

Sources & evidence

ORD record
ord-3d848ebf7c8741e99244ecaff95cf73f
Source dataset
uspto-grants-1987_06
Patent number
US04675392

Reaction notes

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