Sodium Bicarbonate → HCID 87366546, compound

HRID 1670049Notes

Reaction equation

HRID 1670049 reaction equation
[C:1]([O:9][CH:10]([CH2:52][OH:53])[CH2:11][O:12][C@H:13]1[O:42][C@H:41]([CH2:43][O:44][CH2:45][C:46]2[CH:51]=[CH:50][CH:49]=[CH:48][CH:47]=2)[C@H:32]([O:33][CH2:34][C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[C@H:23]([O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C@H:14]1[O:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:54]([O-:57])(O)=O.[Na+]>CCOCC>[C:1]([O:9][CH:10]([CH2:52][O:53][C@H:13]1[O:42][C@H:41]([CH2:43][O:57][CH2:54][C:7]2[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=2)[C@H:32]([O:33][CH2:34][C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[C@H:23]([O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C@H:14]1[O:15][CH2:16][C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1)[CH2:11][O:12][C@H:13]1[O:42][C@H:41]([CH2:43][O:44][CH2:45][C:46]2[CH:47]=[CH:48][CH:49]=[CH:50][CH:51]=2)[C@H:32]([O:33][CH2:34][C:35]2[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=2)[C@H:23]([O:24][CH2:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C@H:14]1[O:15][CH2:16][C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1)(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 516892Sodium BicarbonateHCID 67351474HCID 67351474, compound

Product 1

HCID 87366546HCID 87366546, compoundYield 85.7%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

Trimethylsilyl trifluomethanesulfonate (35 μL, 0.19 mmol) was added dropwise to a stirred solution of the glycerol 39 (376 mg, 0.523 mmol) and O-(2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)trichloroacetimidate (385 mg, 0.562 mmol) in dry ether (20 mL) under argon. After 90 min. solid NaHCO3 (100 mg) was added and the mixture stirred for a further 10 min. The reaction mixture was partitioned between ether (50 mL) and sat. NaHCO3 (40 mL). The aqueous phase was re-extracted with ether (50 mL) and the combined ethereal extract washed with 2M HCl (50 mL), sat. NaHCO3 (40 mL) and H2O (60 mL). After drying (MgSO4) and filtration the solvent was removed at reduced pressure to give the crude product that was purified by column chromatography on silica gel. Gradient elution with ethyl acetate/petroleum ether (10:90→20:80) afforded the title compound 41 (278 mg, 0.224 mmol, 61%) as a thin film; [α]D20 +64.2 (c 1.30, ethyl acetate); 1H NMR (300 MHz, CDCl3) δ 8.05-7.99 (m, 2H), 7.50-7.42 (m, 1H), 7.35-7.10 (m, 42H), 5.57-5.45 (m, 1H), 4.95-4.82 (m, 4H), 4.79-4.30 (m, 15H), 4.00-3.72 (m, 11H), 3.55-3.38 (m, 4H); 13C NMR (75 MHz, CDCl3) δ 166.3, 139.2, 139.1, 139.0, 138.5, 133.4, 130.6, 130.2, 128.7, 128.65, 128.6, 128.1, 127.8, 98.7 (1JCH 168 Hz), 98.3 (1JCH 168 Hz), 79.3, 79.2, 76.9, 75.6, 75.2, 73.8, 73.8, 73.5, 73.4, 72.9, 70.0, 69.3, 69.2, 67.3, 66.7; HRMS-ESI (+ve) (Found: m/z 1258.5888 (MNH4+). C70H84NO14 requires m/z 1258.886).

Workup

  1. customThe reaction mixture was partitioned between ether (50 mL) and sat. NaHCO3 (40 mL)
  2. extractionThe aqueous phase was re-extracted with ether (50 mL)
  3. extractionthe combined ethereal extract
  4. washwashed with 2M HCl (50 mL), sat. NaHCO3 (40 mL) and H2O (60 mL)
  5. customAfter drying
  6. filtration(MgSO4) and filtration the solvent
  7. customwas removed at reduced pressure
  8. customto give the crude product that
  9. customwas purified by column chromatography on silica gel
  10. washGradient elution with ethyl acetate/petroleum ether (10:90→20:80)

Sources & evidence

ORD record
ord-1e3f7d73e7bc488da57c08045bbd3a54
Source dataset
uspto-grants-2011_08
Patent number
US07989602B2

Reaction notes

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