Sodium Azide → HCID 10767878, compound

HRID 552883Notes

Reaction equation

HRID 552883 reaction equation
[C:1]([O:4][C@H:5]1[C@@H:20]([O:21][C:22](=[O:24])[CH3:23])[C@H:19]([O:25][C:26](=[O:28])[CH3:27])[C@@H:18]([CH2:29][O:30][C:31](=[O:33])[CH3:32])[O:17][C@@H:6]1[O:7][CH2:8][CH2:9][O:10][CH2:11][CH2:12][O:13][CH2:14][CH2:15]Cl)(=[O:3])[CH3:2].[N-:34]=[N+:35]=[N-:36].[Na+]>[N+](CCCC)(CCCC)(CCCC)CCCC.[I-].CN(C=O)C.CCOC(C)=O>[C:1]([O:4][C@H:5]1[C@@H:20]([O:21][C:22](=[O:24])[CH3:23])[C@H:19]([O:25][C:26](=[O:28])[CH3:27])[C@@H:18]([CH2:29][O:30][C:31](=[O:33])[CH3:32])[O:17][C@@H:6]1[O:7][CH2:8][CH2:9][O:10][CH2:11][CH2:12][O:13][CH2:14][CH2:15][N:34]=[N+:35]=[N-:36])(=[O:3])[CH3:2]

Participants

6

Reactant 2

HCID 33557Sodium AzideHCID 10743954HCID 10743954, compound

Product 1

HCID 10767878HCID 10767878, compoundYield 86.6%

Reagents, catalysts & solvents 3

HCID 67553Tetrabutylammonium IodideCatalystHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 36 (2.9 g, 5.8 mmol), sodium azide (1.89 g, 29.1 mmol) and nBu4NI (4.3 g, 11.6 mmol) in anhydrous DMF (20 mL) was stirred at 90° C. for 24 h. The solution was cooled to rt then diluted with EtOAc (300 mL). The organic layer was washed with water (3×200 mL), dried (Na2SO4), filtered and evaporated. The oily residue was purified by flash silica gel column chromatography (PE then PE/EtOAc 1:1) to afford 37 (2.54 g, 86%) as a pale yellow oil. 1H NMR (CDCl3, 300 MHz): δ 1.96, 2.02, 2.08, 2.13 (4s, 4×3H, 4×CH3CO), 3.37 (t, 2H, J=5.0 Hz, CH2N3), 3.60-3.72 (m, 9H, OCH2CH2O), 3.74-3.84 (m, 1H, OCH2), 4.00-4.15 (m, 2H, H-5, H-6), 4.27 (dd, 1H, J6′,5=5.1 Hz, J6′,6=12.4 Hz, H-6′), 4.85 (d, 1H, J1,2=1.5 Hz, H-1), 5.20-5.37 (m, 3H, H-2, H-3, H-4). 13C NMR (CDCl3, 75 MHz): δ 20.62, 20.63, 20.7, 20.8 (4s, 4×CH3CO), 50.6 (CH2N3), 62.3 (C-6), 66.0, 68.3, 69.0, 69.5 (4s, C-2 to C-5), 67.2, 69.97, 70.02, 70.6, 70.7 (5s, 5×CH2O), 97.6 (C-1), 169.6, 169:8, 170.0, 170.6 (4s, 4×CH3CO)-[α]D=+34 (c=1/CH2Cl2). ESIMS (positive mode) m/z: 528 [M+Na]+. HRESIMS (positive mode) m/z: calcd for C20H31N3O12Na1 [M+Na]+ 528.1805. found 528.1801.

Workup

  1. washThe organic layer was washed with water (3×200 mL)
  2. dry with materialdried (Na2SO4)
  3. filtrationfiltered
  4. customevaporated
  5. customThe oily residue was purified by flash silica gel column chromatography (PE

Sources & evidence

ORD record
ord-4d63011aa03a4188981b5480ca04ff9d
Source dataset
uspto-grants-2011_05
Patent number
US07951926B2

Reaction notes

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