Reaktion #162029

ord-505bdfe807db4be3922d3ca18e954880

Reaktionsgleichung

CC(=O)OC[C@H]1O[C@@H](N=[N+]=[N-])[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1O[C@H]1O[C@H](COC(C)=O)[C@@H](O[C@H]2O[C@H](COC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]2OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O
azide
CC(=O)OC[C@H]1O[C@@H](N=[N+]=[N-])[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1O[C@H]1O[C@H](COC(C)=O)[C@@H](O[C@H]2O[C@H](COC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]2OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O
2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-β-D-glucopyranosyl azide
C#CCOC1CC[C@@]2(C)C(CC[C@H]3[C@@H]4CC[C@H]([C@H](C)CCCC(C)CO)[C@@]4(C)CC[C@@H]32)C1
3-(prop-2-ynyloxy)cholestanol
ClC(Cl)Cl
CHCl3
O=C1O[C@H]([C@@H](O)CO)C([O-])=C1O.[Na+]
sodium ascorbate
→
CC(=O)OC[C@H]1O[C@@H](n2cc(CO[C@H]3CC[C@@]4(C)C(CC[C@H]5[C@@H]6CC[C@H]([C@H](C)CCCC(C)C)[C@@]6(C)CC[C@@H]54)C3)nn2)[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1O[C@H]1O[C@H](COC(C)=O)[C@@H](O[C@H]2O[C@H](COC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]2OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O
triazole
Ausbeute 68.0%
CC(=O)OC[C@H]1O[C@@H](n2cc(CO[C@H]3CC[C@@]4(C)C(CC[C@H]5[C@@H]6CC[C@H]([C@H](C)CCCC(C)C)[C@@]6(C)CC[C@@H]54)C3)nn2)[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1O[C@H]1O[C@H](COC(C)=O)[C@@H](O[C@H]2O[C@H](COC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]2OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O
4-(Cholestan-3β-yloxymethyl)[1,2,3]triazol-1-yl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-1-deoxy-β-D-glucopyranoside
Ausbeute 68.0%

Edukte

—
aqueous solution
—
aqueous solution
CC(=O)OC[C@H]1O[C@@H](N=[N+]=[N-])[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1O[C@H]1O[C@H](COC(C)=O)[C@@H](O[C@H]2O[C@H](COC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]2OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O
azide
CC(=O)OC[C@H]1O[C@@H](N=[N+]=[N-])[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1O[C@H]1O[C@H](COC(C)=O)[C@@H](O[C@H]2O[C@H](COC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]2OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O
2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-α-D-glucopyranosyl-(1→4)-2,3,6-tri-O-acetyl-β-D-glucopyranosyl azide
C#CCOC1CC[C@@]2(C)C(CC[C@H]3[C@@H]4CC[C@H]([C@H](C)CCCC(C)CO)[C@@]4(C)CC[C@@H]32)C1
3-(prop-2-ynyloxy)cholestanol
ClC(Cl)Cl
CHCl3
O=C1O[C@H]([C@@H](O)CO)C([O-])=C1O.[Na+]
sodium ascorbate

Reagenzien

O=S(=O)([O-])[O-].[Cu+2]
CuSO4

Lösungsmittel

CC(C)(C)O
t-BuOH

Reaktionsbedingungen

Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    SonstigeThe solvent was evaporated
  2. 2
    Sonstigethe residue purified by column chromatography (SiO2: Hexane to 2:3 Hexane:EtOAc)

Vorschrift

The azide 73 (200 mg, 211 μmol), 3-(prop-2-ynyloxy)cholestanol (3 equiv., 267 mg), CHCl3 (2 mL), t-BuOH (2 mL), CuSO4 (50 μL of a 0.3 M aqueous solution) and sodium ascorbate (62.5 μL of a 1M aqueous solution) was stirred vigorously overnight at r.t. The solvent was evaporated and the residue purified by column chromatography (SiO2: Hexane to 2:3 Hexane:EtOAc) to yield the triazole 74 (197 mg, 68%). 1H NMR (300 MHz, CDCl3) δ 7.66 (s, 1H, triazol-H), 5.85 (d, 1H, J1,2=9.3, H-1I), 5.46-5.27 (m, 6H, H-1II, H-1II, H-2I, H-4III, H-3II, H-3III), 5.03 (dd, 1H, J3,2=9.8, J3,4=9.8, H-3I), 4.82 (dd, 1H, J2,1=4.1, J2,3=10.3, H-2), 4.72 (dd, 1H, H-2), 4.63 (s, 2H, CH2O), 4.47-4.41 (m, 2H), 4.32-3.88 (m, 9H), 3.31 (m, 1H, CHO), 2.12 (s, 6H, OAc), 2.06 (s, 3H, OAc), 2.03 (s, 3H, OAc), 2.00 (s, 3H, OAc), 1.99 (s, 3H, OAc), 1.98 (s, 3H, OAc), 1.96 (s, 3H, OAc), 1.96-0.83 (m, 31H), 1.82 (s, 3H, OAc), 0.85 (d, 3H, J=6.7, CH3), 0.82 (m, 6H, CH3), 0.76 (s, 3H, CH3), 0.60 (s, 3H, CH3).

Quelle

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