Reaktion #162040

ord-85b96dd68e0d44ec9520da90d1db0df2

Reaktionsgleichung

O=C(OC[C@H]1O[C@H](Br)[C@H](OC(=O)c2ccccc2)[C@@H](OC(=O)c2ccccc2)[C@@H]1O[C@H]1O[C@H](COC(=O)c2ccccc2)[C@@H](O[C@H]2O[C@H](COC(=O)c3ccccc3)[C@@H](OC(=O)c3ccccc3)[C@H](OC(=O)c3ccccc3)[C@H]2OC(=O)c2ccccc2)[C@H](OC(=O)c2ccccc2)[C@H]1OC(=O)c1ccccc1)c1ccccc1
Bromide
O=C(OC[C@H]1O[C@H](Br)[C@H](OC(=O)c2ccccc2)[C@@H](OC(=O)c2ccccc2)[C@@H]1O[C@H]1O[C@H](COC(=O)c2ccccc2)[C@@H](O[C@H]2O[C@H](COC(=O)c3ccccc3)[C@@H](OC(=O)c3ccccc3)[C@H](OC(=O)c3ccccc3)[C@H]2OC(=O)c2ccccc2)[C@H](OC(=O)c2ccccc2)[C@H]1OC(=O)c1ccccc1)c1ccccc1
2,3,4,6-Tetra-O-benzoyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-benzoyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-benzoyl-α-D-glucopyranosyl bromide
N#C[S-].[K+]
KSCN
→
O=C(OC[C@H]1O[C@@H](N=C=S)[C@H](OC(=O)c2ccccc2)[C@@H](OC(=O)c2ccccc2)[C@@H]1O[C@H]1O[C@H](COC(=O)c2ccccc2)[C@@H](O[C@H]2O[C@H](COC(=O)c3ccccc3)[C@@H](OC(=O)c3ccccc3)[C@H](OC(=O)c3ccccc3)[C@H]2OC(=O)c2ccccc2)[C@H](OC(=O)c2ccccc2)[C@H]1OC(=O)c1ccccc1)c1ccccc1
white solid
Ausbeute 64.7%
O=C(OC[C@H]1O[C@@H](N=C=S)[C@H](OC(=O)c2ccccc2)[C@@H](OC(=O)c2ccccc2)[C@@H]1O[C@H]1O[C@H](COC(=O)c2ccccc2)[C@@H](O[C@H]2O[C@H](COC(=O)c3ccccc3)[C@@H](OC(=O)c3ccccc3)[C@H](OC(=O)c3ccccc3)[C@H]2OC(=O)c2ccccc2)[C@H](OC(=O)c2ccccc2)[C@H]1OC(=O)c1ccccc1)c1ccccc1
2,3,4,6-Tetra-O-benzoyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-benzoyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-benzoyl-β-D-glucopyranosyl isothiocyanate
Ausbeute 64.7%

Edukte

O=C(OC[C@H]1O[C@H](Br)[C@H](OC(=O)c2ccccc2)[C@@H](OC(=O)c2ccccc2)[C@@H]1O[C@H]1O[C@H](COC(=O)c2ccccc2)[C@@H](O[C@H]2O[C@H](COC(=O)c3ccccc3)[C@@H](OC(=O)c3ccccc3)[C@H](OC(=O)c3ccccc3)[C@H]2OC(=O)c2ccccc2)[C@H](OC(=O)c2ccccc2)[C@H]1OC(=O)c1ccccc1)c1ccccc1
Bromide
O=C(OC[C@H]1O[C@H](Br)[C@H](OC(=O)c2ccccc2)[C@@H](OC(=O)c2ccccc2)[C@@H]1O[C@H]1O[C@H](COC(=O)c2ccccc2)[C@@H](O[C@H]2O[C@H](COC(=O)c3ccccc3)[C@@H](OC(=O)c3ccccc3)[C@H](OC(=O)c3ccccc3)[C@H]2OC(=O)c2ccccc2)[C@H](OC(=O)c2ccccc2)[C@H]1OC(=O)c1ccccc1)c1ccccc1
2,3,4,6-Tetra-O-benzoyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-benzoyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-benzoyl-α-D-glucopyranosyl bromide
N#C[S-].[K+]
KSCN

Reagenzien

CCCC[N+](CCCC)(CCCC)CCCC.[I-]
Bu4NI

Lösungsmittel

CC#N
acetonitrile

Reaktionsbedingungen

Temperatur
75°CELSIUS
Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    SonstigeThe solvent was evaporated
  2. 2
    Waschenwashed with NaHCO3(sat.)
  3. 3
    Trocknenbefore being dried (Na2SO4)
  4. 4
    Sonstigethe solvent was evaporated
  5. 5
    SonstigeThe crude product was purified

Vorschrift

Bromide 84 (1.8 g, 1.12 mmol), KSCN (3 equiv., 326 mg), molecular sieves and Bu4NI (cat.) were taken up in dry acetonitrile and stirred at 75° C. overnight. The solvent was evaporated and the residue taken up in DCM and washed with NaHCO3(sat.), before being dried (Na2SO4) and the solvent was evaporated. The crude product was purified using column chromatography (SiO2:Hexane to 35% EtOAc/Hexane, loaded with toluene) to yield 1.15 g of the white solid product (65%). 1H NMR (400 MHz, CDCl3) δ: 8.23-7.12 (m, 50H, Ar), 6.16 (dd, 1H, J3,2=9.6, J3,4=9.6, H-3III), 5.96 (dd, 1H, J3,2=9.6, J3,4=8.2, H-3II), 5.81 (d, 1H, J1,2=4.1, H-1III), 5.75-5.68 (m, 2H, H-3I, H-4III), 5.65 (d, 1H, J1,2=4.1, H-1II), 5.40 (dd, 1H, J2,1=8.2, J2,3=8.2, H-2I), 5.32 (dd, 1H, J2,1=4.1, J2,3=10.2, H-2III), 5.28 (d, 1H, J1,2=8.2, H-1I), 5.13 (dd, 1H, J2,1=4.1, J2,3=10.2, H-2II), 5.00 (dd, 1H, H-6I), 4.77 (dd, 1H, H-6II), 4.72-4.65 (m, 2H, H-6I, H-6II), 4.53-4.41 (m, 5H, H-5II, H-5III, H-4I, H-1II, H-6III), 4.30 (dd, 1H, H-6III), 4.13 (ddd, 1H, H-5I).

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US08828952B2uspto-grants-2014_09