Trimethylsilyl triflate → Isohexane ethyl acetate

HRID 130002Notes

Reaction equation

HRID 130002 reaction equation
S1C=CC=C1[C@]1(O[C@H](CO)[C@@H:11]([O:12][C@@H:13]2[O:30][C@H](CO[CH2:33][C:34]3[CH:39]=C[CH:37]=[CH:36][CH:35]=3)[C@H](OC(=O)C)[C@H](OC(=O)C)[C@H:14]2OC(=O)C)[C@H:9](O)[C@H]1NC(=O)C)O.N(CCCCCCO)=[N+]=[N-].FC(F)(F)S(O[Si](C)(C)C)(=O)=O>C(#N)C>[C:13]([O:12][CH2:11][CH3:9])(=[O:30])[CH3:14].[CH3:37][CH2:36][CH2:35][CH:34]([CH3:39])[CH3:33]

Participants

5

Reactant 3

HCID 65367Trimethylsilyl triflateHCID 110517786-Azidohexan-1-olHCID 867491301-Thiophenyl-(2,3,4-tri-O-acetyl-6-O-benzyl-beta-D-galactopyranosyl)-(1-4)-2-deoxy-2-acetamido-beta-D-glucopyranose

Product 1

HCID 21882781Isohexane ethyl acetateYield 65%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

Compound [13] (0.21-2.66 g, 0.54-7.05 mmol) and 6-azidohexanol (0.27-3.54 g, 1.08-14.1 mmol) are dissolved in dry acetonitrile and, at 0° C., molecular sieves (0.2-5 g) and trimethylsilyl trifluoromethanesulfonate (0.02-1.56 g, 1-70 mmol) are added. After the reaction is complete, the mixture is filtered and washed with saturated sodium bicarbonate solution. Concentration results in the crude product which is purified by chromatography on silica gel with an ethyl acetate/isohexane gradient (0.17-2.23 g, 0.35-4.58 mmol, about 65% yield). The product is subsequently taken up in methanol/hydrazine hydrate (1:1) (1-30 ml) and heated at 80° C. until reaction is complete. After evaporation of the solvent, the crude product is taken up in dichloromethane/methanol (1:1) and stirred at 0° C. with acetic anhydride (3.5-45.8 mmol) until reaction is complete. Evaporation is followed by reduction of the azide with hydrogen in the presence of catalytic amounts of palladium on carbon (10%) (0.01-1.5 g) in methanol (0.5-40 ml). The crude product compound [14] obtained after evaporation is purified by gel chromatography on Biogel P2 (0.12-1.54 g, 0.25-3.2 mmol, about 70% yield). FAB-MS: M+H+ =483. 1H-NMR [300 MHz, D2O]: 4.98 (Fuc-H -1), 4.28 (Gal-H-1), 4.33, 3.99-3.38 (m), 2.99, 2.09 (GlcNCOCH3), 1.72-1.32 (O--(CH2)5 --CH2 --N), 1.11 (Fuc-CH3) ppm.

Workup

  1. filtrationthe mixture is filtered
  2. washwashed with saturated sodium bicarbonate solution
  3. concentrationConcentration
  4. customresults in the crude product which

Sources & evidence

ORD record
ord-3a792abbf3dd4219acd95f2b01f24bfe
Source dataset
uspto-grants-1995_11
Patent number
US05470843

Reaction notes

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