Boron trifluoride etherate → p-Methylphenyl 3,4,6-Tri-O-acetyl-2-deoxy-2(2,2,2-trichloroethoxylcarbonylamino)-1-thio-beta-D-glucopyranoside

HRID 1862753Notes

Reaction equation

HRID 1862753 reaction equation
C(O[C@@H]1O[C@H](COC(=O)C)[C@@H](OC(=O)C)[C@H](OC(=O)C)[C@H]1[NH:24][C:25]([O:27][CH2:28][C:29]([Cl:32])([Cl:31])[Cl:30])=[O:26])(=O)C.C1(C)C(S)=CC=CC=1.B(F)(F)F.CCOCC.C(O[C@H:54]1[C@@H:67]([O:68][C:69](=[O:71])[CH3:70])[C@H:66]([O:72][C:73](=[O:75])[CH3:74])[C@@H:65]([CH2:76][O:77][C:78](=[O:80])[CH3:79])[O:64][C@@H:55]1[S:56][C:57]1[CH:62]=[CH:61][C:60]([CH3:63])=[CH:59][CH:58]=1)(=O)C>C(Cl)Cl>[C:69]([O:68][C@H:67]1[C@H:66]([O:72][C:73](=[O:75])[CH3:74])[C@@H:65]([CH2:76][O:77][C:78](=[O:80])[CH3:79])[O:64][C@@H:55]([S:56][C:57]2[CH:62]=[CH:61][C:60]([CH3:63])=[CH:59][CH:58]=2)[C@@H:54]1[NH:24][C:25]([O:27][CH2:28][C:29]([Cl:32])([Cl:31])[Cl:30])=[O:26])(=[O:71])[CH3:70]

Participants

6

Reactant 4

HCID 8000Boron trifluoride etherateHCID 87122-ThiocresolHCID 11038656(2S,3R,4R,5S,6R)-6-(Acetoxymethyl)-3-(((2,2,2-trichloroethoxy)carbonyl)amino)tetrahydro-2H-pyran-2,4,5-triyl triacetateHCID 11775389(2R,3R,4S,5S,6R)-2-(acetoxymethyl)-6-(p-tolylthio)tetrahydro-2H-pyran-3,4,5-triyl triacetate

Product 1

HCID 15497894p-Methylphenyl 3,4,6-Tri-O-acetyl-2-deoxy-2(2,2,2-trichloroethoxylcarbonylamino)-1-thio-beta-D-glucopyranosideYield 89%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

The tittle compound was prepared from 1,3,4,6-tetra-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxylcarbonylamino)-β-D-glucopyranose (Boullanger, P. et al Carbohydr. Res. 1990, 202, 151) (11.8 g, 22.5 mmol), thiocresol (3.07 g, 24.75 mmol) and BF3-Et2O (10 mL) in dry CH2Cl2 (60 mL) by the procedure described above (see compound 1) The crude product was crystallization from ether to give 21 (11.8 g, 89%) as white crystals: m.p. 175-176° C.; [α]D22 +3° (c, 0.5, CHCl3); 1H-NMR (400 MHz, CDCl3) δ 2.00 (s, 3H), 2.01 (s, 3H), 2.09 (s, 3H), 2.35 (s, 3H), 3.71-3.73 (m, 1H), 4.11-4.25 (m, 2H), 4.73 (d, 1H, J=12.0 Hz), 4.79 (d, 1H, J=10.8 Hz), 5.01 (t, 1H, J=9.8 Hz), 5.26 (d, 1H, J=9.8 Hz), 5.31 (d, 1H, J=9.1 Hz), 7.11 (d, 2H, J=8.0 Hz), 7.41 (d, 2H, J=8.0 Hz); 13C-NMR (400 MHz, CDCl3); δ 20.56, 20.61, 20.73, 21.15, 54.93, 62.25, 68.44, 73.14, 74.47, 75.70, 86.65, 95.36, 127.84, 129.71, 133.62, 138.70, 153.85, 169.45, 170.61; HRMS for C22H26NO9SCl3Na (M+Na) calcd 610.0266, found 610.0286. Anal. Calcd for C22H26NO9SCl3: C, 45.03; H, 4.47; N, 2.39. Found: C, 45.46; H, 4.26; N, 2.30.

Workup

  1. customcrystallization from ether

Sources & evidence

ORD record
ord-f9c3a92d4fdb42bb8782001230994e08
Source dataset
uspto-grants-2003_03
Patent number
US06538117B1

Reaction notes

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