Reaktion #90569

Reaktionsgleichung

319

Allyl (2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-β-D-glucopyranosyl)-(1→2)-3,4-di-O-benzyl-α-L-rhamnopyranoside

→

320

Ausbeute 69.2%

(2-acetamido-3,4,6-tri-O-acetyl-2-deoxy-β-D-glucopyranosyl)-(1→2)-3,4-di-O-benzyl-α-L-rhamnopyranose

Ausbeute 69.2%

Lösungsmittel

THF

THF

Reaktionsbedingungen

Aufarbeitung

1. 1
   Sonstigethe resulting red solution was degassed in an argon stream
2. 2
   SonstigeHydrogen was then bubbled through the solution
3. 3
   SonstigeThe solution was then degassed again in an argon stream
4. 4
   workup.ADDITIONadded
5. 5
   EinengenThe mixture was concentrated
6. 6
   workup.ADDITIONwater (10 mL) was added
7. 7
   workup.STIRRINGThe mixture was stirred for 2 h at rt
8. 8
   Einengenconcentrated
9. 9
   Waschenwashed three times with sat. aq. KI
10. 10
    SonstigeThe organic phase was dried
11. 11
    Einengenconcentrated
12. 12
    SonstigeThe residue was purified by column chromatography (cyclohexane-EtOAc 3:7)

Vorschrift

1,5-Cyclooctadiene-bis(methyldiphenylphosphine)iridium hexafluorophosphate (10 mg, 12 μmol) was dissolved THF (10 mL), and the resulting red solution was degassed in an argon stream. Hydrogen was then bubbled through the solution, causing the colour to change to yellow. The solution was then degassed again in an argon stream. A solution of 319 (830 mg, 1.16 mmol) in THF (40 mL) was degassed and added. The mixture was stirred at rt overnight. The mixture was concentrated. The residue was taken up in acetone (90 mL), and water (10 mL) was added. Mercuric chloride (475 mg, 1.75 mmol) and mercuric oxide (504 mg, 2.32 mmol) were added to the mixture, protected from light. The mixture was stirred for 2 h at rt, then concentrated. The residue was taken up in CH2Cl2 and washed three times with sat. aq. KI, then with brine. The organic phase was dried and concentrated. The residue was purified by column chromatography (cyclohexane-EtOAc 3:7) to give 320 (541 mg, 69%) as a white foam; [α]D+16° (c 1.0, CHCl3): 1H NMR: δ 7.35-7.05 (m, 10H, Ph), 5.50 (d, 1H, J2,NH=8.2 Hz, NHD), 5.22 (d, 1H, J1,2=1.1 Hz, H-1A), 5.06 (pt, 1H, J3,4=J4,5=9.5 Hz, H-4D), 5.00 (pt, 1H, J2,3=9.5 Hz, H-3D), 4.85-4.60 (m, 4H, CH2Ph), 4.56 (d, 1H, J1,2=7.0 Hz, H-1D), 4.22-4.13 (m, 2H, J5,6=4.5, J6a,6b=12.3 Hz, H-6aD, 6bD), 4.03 (m, 1H, H-2D), 4.00 (dq, 1H, J4,5=9.5, J5,6=6.2 Hz, H-5A), 3.96 (dd, 1H, J2,3=3.3 Hz, H-2A), 3.90 (dd, 1H, J3,4=9.5 Hz, H-3A), 3.60 (m, 1H, H-5D), 3.48 (d, 1H, J1,OH=3.5 Hz, OH), 3.40 (pt, 1H, H-4A), 2.08, 2.03, 2.01 (3s, 9H, OAc), 1.65 (s, 3H, NHAc), 1.30 (d, 3H, H-6A); 13C NMR: δ 171.2, 171.0, 170.4, 169.6 (C═O), 138.2-128.0 (Ph), 103.3 (C-1D), 94.1 (C-1A), 81.4 (C-4A), 79.9 (C-2A), 78.7 (C-3A), 75.8, 73.9 (2C, CH2Ph), 73.6 (C-3D), 72.4 (C-5D), 68.7 (C-4D), 68.2 (C-5A), 62.4 (C-6D), 54.5 (C-2D), 23.3 (NHAc), 21.1, 21.0, 21.0 (3C, OAc), 18.3 (C-6A). FAB-MS for C34H43NO13 (M, 673.2), m/z 696.3 [M+Na]+. Anal. Calcd for C34H43NO13: C, 60.61; H, 6.43; N, 2.08. Found: C, 60.46; H, 6.61; N, 1.95.

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