Sodium Bicarbonate → 3-(3-(((9H-fluoren-9-yl)methoxy)carbonylamino)propanamido)-4-((2S,3R,4S,5S,6S)-3,4,5-triacetoxy-6-(methoxycarbonyl)-tetrahydro-2H-pyran-2-yloxy)benzyl 2-(3-hydroxypropyl)oxazolidine-3-carboxylate

HRID 1664237Notes

Reaction equation

HRID 1664237 reaction equation
[Si]([O:18][CH2:19][CH2:20][CH2:21][CH:22]1[N:26]([C:27]([O:29][CH2:30][C:31]2[CH:36]=[CH:35][C:34]([O:37][C@H:38]3[C@H:43]([O:44][C:45](=[O:47])[CH3:46])[C@@H:42]([O:48][C:49](=[O:51])[CH3:50])[C@H:41]([O:52][C:53](=[O:55])[CH3:54])[C@@H:40]([C:56]([O:58][CH3:59])=[O:57])[O:39]3)=[C:33]([NH:60][C:61](=[O:82])[CH2:62][CH2:63][NH:64][C:65]([O:67][CH2:68][CH:69]3[C:81]4[CH:80]=[CH:79][CH:78]=[CH:77][C:76]=4[C:75]4[C:70]3=[CH:71][CH:72]=[CH:73][CH:74]=4)=[O:66])[CH:32]=2)=[O:28])[CH2:25][CH2:24][O:23]1)(C(C)(C)C)(C1C=CC=CC=1)C1C=CC=CC=1.C(=O)(O)[O-].[Na+]>C1COCC1.N1C=CC=CC=1>[OH:18][CH2:19][CH2:20][CH2:21][CH:22]1[N:26]([C:27]([O:29][CH2:30][C:31]2[CH:36]=[CH:35][C:34]([O:37][C@H:38]3[C@H:43]([O:44][C:45](=[O:47])[CH3:46])[C@@H:42]([O:48][C:49](=[O:51])[CH3:50])[C@H:41]([O:52][C:53](=[O:55])[CH3:54])[C@@H:40]([C:56]([O:58][CH3:59])=[O:57])[O:39]3)=[C:33]([NH:60][C:61](=[O:82])[CH2:62][CH2:63][NH:64][C:65]([O:67][CH2:68][CH:69]3[C:70]4[CH:71]=[CH:72][CH:73]=[CH:74][C:75]=4[C:76]4[C:81]3=[CH:80][CH:79]=[CH:78][CH:77]=4)=[O:66])[CH:32]=2)=[O:28])[CH2:25][CH2:24][O:23]1

Participants

5

Reactant 2

HCID 516892Sodium BicarbonateHCID 598165413-(3-(((9H-fluoren-9-yl)methoxy)carbonylamino)propanamido)-4-((2S,3R,4S,5S,6S)-3,4,5-triacetoxy-6-(methoxycarbonyl)-tetrahydro-2H-pyran-2-yloxy)benzyl 2-(3-(tert-butyldiphenylsilyloxy)propyl)oxazolidine-3-carboxylate

Product 1

HCID 866234303-(3-(((9H-fluoren-9-yl)methoxy)carbonylamino)propanamido)-4-((2S,3R,4S,5S,6S)-3,4,5-triacetoxy-6-(methoxycarbonyl)-tetrahydro-2H-pyran-2-yloxy)benzyl 2-(3-hydroxypropyl)oxazolidine-3-carboxylateYield 94.6%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a mixture of the silyl ether 13 (52 mg, 0.042 mmol) in THF (2 mL) and pyridine (2 mL) was added HF-pyridine complex (400 μL). The reaction mixture was stirred for 3 h and was poured into saturated aqueous sodium bicarbonate and was extracted with ethyl acetate (3×100 mL). The combined extracts were washed with water and brine and dried over sodium sulfate, before being filtered and concentrated. The resulting oil was purified via radial chromatography on a 1 plate eluting with 5% methanol in dichloromethane to give 36 mg (86%) of a solid residue: 1H NMR (CD3OD); δ1.55 (bs, 2H), 1.68 (m, 1H), 1.87 (m, 1H), 1.95 (s, 3H), 2.01 (m, 6H), 2.67 (oct, 2H, J=6.8 Hz), 3.30 (m, 1H), 3.50 (m, 3H), 3.65 (m, 1H), 3.69 (m, 3H), 3.82 (q, 1H, J=8.0 Hz), 4.01 (m, 1H), 4.23 (m, 1H, J=7.0 Hz), 4.25-4.40 (m, 2H), 4.47 (d, 1H, J=10.0 Hz), 5.0-5.15 (m, 3H), 5.19 (t, 1H, J=9.8 Hz), 5.28 (dd, 1H, J=6.0, 9.6 Hz), 5.39 (d, 1H, J=7.6 Hz), 5.49 (m, 3H), 7.11 (m, 2H), 7.17-7.32 (m, 3H), 7.34 (t, 2H, J=7.4 Hz), 7.62 (d, 2H, J=7.6 Hz), 7.77 (d, 2H, J=7.6 Hz), 8.07 (s, 1H); LC-MS m/z (ES+), 927.87 (M+Na+)+, 9.79 min.

Workup

  1. additionwas added HF-pyridine complex (400 μL)
  2. extractionwas extracted with ethyl acetate (3×100 mL)
  3. washThe combined extracts were washed with water and brine
  4. dry with materialdried over sodium sulfate
  5. filtrationbefore being filtered
  6. concentrationconcentrated
  7. customThe resulting oil was purified via radial chromatography on a 1 plate
  8. washeluting with 5% methanol in dichloromethane

Sources & evidence

ORD record
ord-f939f9eba3824310b46377019e462256
Source dataset
uspto-grants-2011_10
Patent number
US08039273B2

Reaction notes

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