Nitrogen → HCID 21355755, compound

HRID 397216Notes

Reaction equation

HRID 397216 reaction equation
[Si]([O:8][C:9]1[CH:14]=[CH:13][CH:12]=[C:11]([O:15][Si](C(C)(C)C)(C)C)[C:10]=1[C:23]1[C:24]([C@H](O)CC=C)=[C:25]2[C:30](=[CH:31][CH:32]=1)[NH:29][C:28]([CH3:34])([CH3:33])[CH:27]=[C:26]2[CH3:35])(C(C)(C)C)(C)C.N#N.CCCC[N+](CCCC)(CCCC)CCCC.[F-].[NH4+].[Cl-].[CH2:63]1[CH2:67][O:66][CH2:65][CH2:64]1>C(O)(=O)C.CC(OC)(C)C>[OH:66][C@@H:65]([N:29]1[C:30]2[C:25](=[CH:24][C:23]([C:10]3[C:11]([OH:15])=[CH:12][CH:13]=[CH:14][C:9]=3[OH:8])=[CH:32][CH:31]=2)[C:26]([CH3:35])=[CH:27][C:28]1([CH3:34])[CH3:33])[CH2:64][CH:63]=[CH2:67]

Participants

8

Reactant 5

HCID 947NitrogenHCID 8028Tetrahydrofuran2×HCID 25517Ammonium ChlorideHCID 2724141Tetrabutylammonium FluorideHCID 11180729HCID 11180729, compound

Product 1

HCID 21355755HCID 21355755, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 15413tert-Butyl methyl etherSolvent

Procedure

The product from Example 4 (1.0 g, 1.7 mmol) in THF (15 mL) and acetic acid (0.1 mL) was purged with N2 for 10 minutes at room temperature and then treated with a 1.0 M solution of TBAF in THF (7.6 mL). The reaction mixture was stirred at room temperature overnight under N2. HPLC indicated that the de-silylation was complete. The reaction mixture was poured into a solution of saturated NH4Cl (30 mL) and stirred briefly before MTBE (30 mL) was added. After stirring for 5 minutes, the organic layer was separated, washed with brine, dried over Na2SO4 and concentrated to dryness to give light yellow solid. The solid was then recrystallized with EtOAc/heptane to give the title compound (520 mg) as an off-white solid. 1H NMR [(CD3)2SO] δ1.10(3H, s), 1.22(3H, s), 2.17(3H, s), 2.23 (2H, m), 4.76˜4.80 (3H, m), 5.12 (1H, d), 5.40 (1H, br), 5.52(1H, m), 5.88 (1H, br), 6.43 (1H, dd), 6.53 (2H, m), 6.93 (1H, t), 8.92 (1H, s), 9.09 (1H, s); 13C NMR [(CD3)2SO]δ23.3, 27.2, 28.6, 39.8, 48.9, 71.2, 107.1, 107.4, 113.0, 115.3, 119.3, 122.2, 122.5, 127.6, 129.6, 131.6, 132.2, 136.8, 138.3, 145.0, 154.8, 155.9; ESI-MS: m/z 352 (M+H)+; HRMS-FAB: calcd 351.1834, found 351.1829.

Workup

  1. additionwas added
  2. stirringAfter stirring for 5 minutes
  3. customthe organic layer was separated
  4. washwashed with brine
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated to dryness
  7. customto give light yellow solid
  8. customThe solid was then recrystallized with EtOAc/heptane

Sources & evidence

ORD record
ord-992446118f94474294b4a1d39a7ca1ff
Source dataset
uspto-grants-2003_08
Patent number
US06608216B2

Reaction notes

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