Reaktion #162015

ord-656719492efc4a09a5ea0a24e13018c3

Reaktionsgleichung

CC(=O)OC[C@H]1O[C@H](O[C@@H]2[C@H](OC(C)=O)[C@@H](O[C@@H]3[C@H](OC(C)=O)[C@@H](O[C@@H]4[C@H](OC(C)=O)[C@@H](O[C@@H]5[C@@H](OCCCCCCCCCCCCN=[N+]=[N-])O[C@H](COC(C)=O)[C@@H](OC(C)=O)[C@@H]5OC(C)=O)O[C@H](COC(C)=O)[C@H]4OC(C)=O)O[C@H](COC(C)=O)[C@H]3OC(C)=O)O[C@H](COC(C)=O)[C@H]2OC(C)=O)[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1OC(C)=O
azide
CC(=O)OC[C@H]1O[C@H](O[C@@H]2[C@H](OC(C)=O)[C@@H](O[C@@H]3[C@H](OC(C)=O)[C@@H](O[C@@H]4[C@H](OC(C)=O)[C@@H](O[C@@H]5[C@@H](OCCCCCCCCCCCCN=[N+]=[N-])O[C@H](COC(C)=O)[C@@H](OC(C)=O)[C@@H]5OC(C)=O)O[C@H](COC(C)=O)[C@H]4OC(C)=O)O[C@H](COC(C)=O)[C@H]3OC(C)=O)O[C@H](COC(C)=O)[C@H]2OC(C)=O)[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1OC(C)=O
12-Azidododecyl 2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl-(1→3)-2,4,6-tri-O-acetyl-α-D-mannopyranosyl-(1→3)-2,4,6-tri-O-acetyl-α-D-mannopyranosyl-(1→3)-2,4,6-tri-O-acetyl-α-D-mannopyranosyl-(1→2)-3,4,6-tri-O-acetyl-α-D-mannopyranoside
C#Cc1cccc2ccccc12
1-ethynylnaphthalene
O=C1O[C@H]([C@@H](O)CO)C([O-])=C1O.[Na+]
sodium ascorbate
→
CC(=O)OC[C@H]1O[C@H](O[C@@H]2[C@H](OC(C)=O)[C@@H](O[C@@H]3[C@H](OC(C)=O)[C@@H](O[C@@H]4[C@H](OC(C)=O)[C@@H](O[C@@H]5[C@@H](OCCCCCCCCCCCCn6cc(-c7cccc8ccccc78)nn6)O[C@H](COC(C)=O)[C@@H](OC(C)=O)[C@@H]5OC(C)=O)O[C@H](COC(C)=O)[C@H]4OC(C)=O)O[C@H](COC(C)=O)[C@H]3OC(C)=O)O[C@H](COC(C)=O)[C@H]2OC(C)=O)[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1OC(C)=O
naphthyltriazole
Ausbeute 26.0%
CC(=O)OC[C@H]1O[C@H](O[C@@H]2[C@H](OC(C)=O)[C@@H](O[C@@H]3[C@H](OC(C)=O)[C@@H](O[C@@H]4[C@H](OC(C)=O)[C@@H](O[C@@H]5[C@@H](OCCCCCCCCCCCCn6cc(-c7cccc8ccccc78)nn6)O[C@H](COC(C)=O)[C@@H](OC(C)=O)[C@@H]5OC(C)=O)O[C@H](COC(C)=O)[C@H]4OC(C)=O)O[C@H](COC(C)=O)[C@H]3OC(C)=O)O[C@H](COC(C)=O)[C@H]2OC(C)=O)[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1OC(C)=O
12-(4-Naphthalen-1-yl-[1,2,3]triazol-1-yl)dodecyl 2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl-(1→3)-2,4,6-tri-O-acetyl-α-D-mannopyranosyl-(1→3)-2,4,6-tri-O-acetyl-α-D-mannopyranosyl-(1→3)-2,4,6-tri-O-acetyl-α-D-mannopyranosyl-(1→2)-3,4,6-tri-O-acetyl-α-D-mannopyranoside
Ausbeute 26.0%

Edukte

CC(=O)OC[C@H]1O[C@H](O[C@@H]2[C@H](OC(C)=O)[C@@H](O[C@@H]3[C@H](OC(C)=O)[C@@H](O[C@@H]4[C@H](OC(C)=O)[C@@H](O[C@@H]5[C@@H](OCCCCCCCCCCCCN=[N+]=[N-])O[C@H](COC(C)=O)[C@@H](OC(C)=O)[C@@H]5OC(C)=O)O[C@H](COC(C)=O)[C@H]4OC(C)=O)O[C@H](COC(C)=O)[C@H]3OC(C)=O)O[C@H](COC(C)=O)[C@H]2OC(C)=O)[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1OC(C)=O
azide
CC(=O)OC[C@H]1O[C@H](O[C@@H]2[C@H](OC(C)=O)[C@@H](O[C@@H]3[C@H](OC(C)=O)[C@@H](O[C@@H]4[C@H](OC(C)=O)[C@@H](O[C@@H]5[C@@H](OCCCCCCCCCCCCN=[N+]=[N-])O[C@H](COC(C)=O)[C@@H](OC(C)=O)[C@@H]5OC(C)=O)O[C@H](COC(C)=O)[C@H]4OC(C)=O)O[C@H](COC(C)=O)[C@H]3OC(C)=O)O[C@H](COC(C)=O)[C@H]2OC(C)=O)[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1OC(C)=O
12-Azidododecyl 2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl-(1→3)-2,4,6-tri-O-acetyl-α-D-mannopyranosyl-(1→3)-2,4,6-tri-O-acetyl-α-D-mannopyranosyl-(1→3)-2,4,6-tri-O-acetyl-α-D-mannopyranosyl-(1→2)-3,4,6-tri-O-acetyl-α-D-mannopyranoside
C#Cc1cccc2ccccc12
1-ethynylnaphthalene
O=C1O[C@H]([C@@H](O)CO)C([O-])=C1O.[Na+]
sodium ascorbate

Reagenzien

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

Lösungsmittel

CC(C)(C)O
t-butanol

Reaktionsbedingungen

Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    SonstigeThe mixture was then evaporated onto silica gel
  2. 2
    Sonstigepurified by flash column chromatography (1×18 cm, gradient elution with hexane-ethyl acetate 6:1, 4:1, 2:1, 1:1, 1:2 to 1:3)

Vorschrift

In a 1 mL HPLC sample vial was loaded the azide 5 (86 mg, 50.3 μmol), t-butanol (100 μL, 0.4 M), 1-ethynylnaphthalene (83 μmol, 2 eq), copper sulfate solution (0.3 M in water, 14 μL, 4.2 μmol, 10 mol %) and sodium ascorbate solution (1 M in water, 12.4 μL, 12.4 μmol, 30 mol %) in that order. The mixture was stirred at room temperature for 11 days. The mixture was then evaporated onto silica gel and purified by flash column chromatography (1×18 cm, gradient elution with hexane-ethyl acetate 6:1, 4:1, 2:1, 1:1, 1:2 to 1:3) to give the naphthyltriazole 9 as a colourless gum (24.2 mg, 26%). 1H NMR (CDCl3, 400 MHz) δ 8.38-8.33 (m, 1H), 7.92-7.86 (m, 2H), 7.80 (s, 1H, triazole-CH), 7.72 (dd, 1H, J=7.3, 1.5), 7.54-7.48 (m, 3H), 5.31-5.15 (m, 8H), 5.03-4.87 (m, 8H), 4.47 (t, 2H, J=7.3, N—CH2), 4.30-3.77 (m, 19H), 3.64 (dt, 1H, J=9.7, 6.8, OCH2), 3.40 (dt, 1H, J=9.7, 6.8, OCH2), 2.17, 2.16, 2.16, 2.13, 2.12, 2.11, 2.11, 2.10, 2.09, 2.07, 2.06, 2.05, 2.02, 2.00, 1.97, 1.57 (15 s, each 3H, except 2.100 (6H), 16×Ac), 2.07-1.95 (m, overlapped with Ac singlets, 2H, CH2), 1.57 (m, 1H, CH2), 1.42-1.23 (m, 16H, 8×CH2).

Quelle

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