Carbon Tetrachloride → 1,3,4,6-Tetra-O-acetyl-2-azido-2-deoxyhexopyranose

HRID 2227878Notes

Reaction equation

[C:1]([O:4][C@@H:5]1[O:26][C@H:25]([CH2:27][O:28][C:29](=[O:31])[CH3:30])[C@@H:20]([O:21][C:22](=[O:24])[CH3:23])[C@H:15]([O:16][C:17](=[O:19])[CH3:18])[C@@H:6]1OS(C(F)(F)F)(=O)=O)(=[O:3])[CH3:2].C[Si]([N:36]=[N+:37]=[N-:38])(C)C.CCCC[N+](CCCC)(CCCC)CCCC.[F-].C(Cl)(Cl)(Cl)Cl>C1COCC1>[C:1]([O:4][C@@H:5]1[O:26][C@H:25]([CH2:27][O:28][C:29](=[O:31])[CH3:30])[C@@H:20]([O:21][C:22](=[O:24])[CH3:23])[C@H:15]([O:16][C:17](=[O:19])[CH3:18])[C@H:6]1[N:36]=[N+:37]=[N-:38])(=[O:3])[CH3:2]

Participants

Conditions

Temperature: 25 °C

Procedure

1,3,4,6-Tetra-O-acetyl-2-O-trifluormethanesulfonyl-β-D-mannopyranose (6) (53 mg, 0.11 mmol) was dissolved at 25° C. in 3 mL of THF. Trimethylsilyl azide (19 μL, 0.15 mmol) was added via syringe followed by TBAF (150 μL, 0.15 mmol). The solution was stirred at 25° C. for 22 h. The reaction mixture was filtered through a plug of silica gel and concentrated in vacuo to give a yellow oil which was chromatographed (2:1, hexane/EtOAc) to afford 30 mg (73%) of β-anomer as a colorless oil. IR (CCl4) 2113, 1762; 1H NMR (CDCl3) 5.56 (d, J=8.8), 5.10 (t, J=9.5), 5.05 (t, J=9.5), 4.31 (dd, J=4.8, 12.5), 4.09 (dd, J=12.5), 3.79 (ddd, J=9.5, 4.8, 2.0), 3.65 (dd, J=9.5, 8.8), 2.18 (s, 3H), 2.08 (s, 3H), 2.06 (s, 3H), 2.01 (s, 3H). The spectra for the anomeric mixture has been previously reported (Vasella, A. et al., Helv. Chim. Acta 74:2073-2077 (1991)).

Workup

filtrationThe reaction mixture was filtered through a plug of silica gel
concentrationconcentrated in vacuo
customto give a yellow oil which
customwas chromatographed (2:1, hexane/EtOAc)
customto afford 30 mg (73%) of β-anomer as a colorless oil

Sources & evidence

ORD record: ord-682ab660424a462c9bebc0cbd54a416d
Source dataset: uspto-grants-2002_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06414173B1

Reaction notes

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