Tetrahydrofuran → HCID 22610872, compound

HRID 843518Notes

Reaction equation

HRID 843518 reaction equation
[H-].[Na+].[N:3]([CH2:6][C:7]([CH2:11][N:12]=[N+:13]=[N-:14])([CH3:10])[CH2:8]O)=[N+:4]=[N-:5].Br[CH2:16][CH2:17][O:18][Si:19]([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:21])[CH3:20].C1C[O:29][CH2:28]C1>[N+](CCCC)(CCCC)(CCCC)CCCC.[I-]>[N:3]([CH2:6][C:7]([CH2:11][N:12]=[N+:13]=[N-:14])([CH3:10])[CH2:8][C:28](=[O:29])[CH2:16][CH2:17][O:18][Si:19]([C:22]([CH3:25])([CH3:24])[CH3:23])([CH3:21])[CH3:20])=[N+:4]=[N-:5]

Participants

6

Reactant 4

HCID 8028TetrahydrofuranHCID 24758Sodium hydrideHCID 3608067(2-Bromoethoxy)-tert-butyldimethylsilaneHCID 14128692HCID 14128692, compound

Product 1

HCID 22610872HCID 22610872, compoundYield 55%

Reagents, catalysts & solvents 1

HCID 67553Tetrabutylammonium IodideCatalyst

Procedure

NaH (480 mg, 80% dispersion, 16 mmol) was added to a solution of 3 (2.10 g, 12.4 mmol) and Bu4NI (228 mg, 0.62 mmol) in THF (50 mL) under N2. After 20 min 2-bromo-1-O-tert-butyldimethylsilylethanol (4.6 g, 19.2 mmol) was added dropwise. After 22 h, the solvent was reduced and the residue partitioned between ether (150 mL) and water (40 mL). The aqueous layer was reextracted with ether (50 mL×2). The organic fractions were combined, washed with brine (40 mL), dried (MgSO4), filtered and the solvent removed. The residue was purified by flash chromatography (EtOAc:hexane, 1:19) to give 5,5-bis(azidomethyl)-1-O-tert-butyldimethylsilyl-3-oxo-hexan-1-ol (5) (2.24 g, 55%) as a colorless oil; IR (film) 2100 (N3) cm−1; 1H NMR (CDCl3, 400 MHz) δ0.05 (s, 6H, Si(CH3)2), 0.88 (s, 9H, SiC(CH3)3), 0.94 (s, 3H, H-6), 3.24 (d, 2H, JH,H′ 11.9 Hz, —CHH′N—×2), 3.26 (s, 2H, H-4), 3.28 (d, 2H, JH,H′ 12.1 Hz, —CHH′N—×2), 3.47-3.50 (m, 2H, H-2), 3.72-3.74 (m, 2H, H-1); 13C NMR (CDCl3, 100 MHz) δ−5.3 (Si(CH3)2), 18.1 (SiC(CH3)), 18.4 (C-6), 25.9 (C(CH3)3), 41.2 (C-5), 55.8 (—CH2N—), 62.6, 73.0, 73.7 (C-1, C-2, C-4); MS m/z (FAB+): 351 (M+Na+, 3), 329 (M+H+, 45).

Workup

  1. customthe residue partitioned between ether (150 mL) and water (40 mL)
  2. washwashed with brine (40 mL)
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. customthe solvent removed
  6. customThe residue was purified by flash chromatography (EtOAc:hexane, 1:19)

Sources & evidence

ORD record
ord-548f9c9047504286a760dc4b8951da92
Source dataset
uspto-grants-2002_04
Patent number
US06379942B1

Reaction notes

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