反応 #90567

反応方程式

317

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

→

318

収率 83.1%

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

収率 83.1%

溶媒

tetrahydrofuran

tetrahydrofuran

反応条件

後処理

1. 1
   その他the resulting red solution was degassed in an argon stream
2. 2
   その他Hydrogen was then bubbled through the solution
3. 3
   その他The solution was then degassed again in an argon stream
4. 4
   workup.ADDITIONadded
5. 5
   濃縮The mixture was concentrated
6. 6
   workup.ADDITIONwater (3 mL) was added
7. 7
   workup.STIRRINGThe mixture was stirred for 2 h at rt
8. 8
   濃縮concentrated
9. 9
   洗浄washed three limes with sat. aq. KI
10. 10
    その他The organic phase was dried
11. 11
    濃縮concentrated
12. 12
    その他The residue was purified by column chromatography (cyclohexane-EtOAc 4:1)

実験手順

1,5-Cyclooctadiene-bis(methyldiphenylphosphine)iridium hexafluorophosphate (120 mg, 140 μmol) was dissolved tetrahydrofuran (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 317 (1.46 g, 1.75 mmol) in tetrahydrofuran (20 mL) was degassed and added. The mixture was stirred at rt overnight. The mixture was concentrated. The residue was taken up in acetone (27 mL), and water (3 mL) was added. Mercuric bromide (949 mg, 2.63 mmol) and mercuric oxide (761 mg, 3.5 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 limes with sat. aq. KI, then with brine. The organic phase was dried and concentrated. The residue was purified by column chromatography (cyclohexane-EtOAc 4:1) to give 318 (1.13 g, 81%) as a white foam. [α]D+4° (c 1, CHCl3). 1H NMR: δ 7.35-7.05 (m, 10H, Ph), 6.74 (d, 1H, J2,NH=8.5 Hz, NHD), 5.10 (d, 1H, J1,2=1.1 Hz, H-1A), 5.02 (m, 2H, H-3D, 4D), 4.80-4.50 (m, 4H, CH2Ph), 4.61 (d, 1H, J1,2=8.5 Hz, H-1D), 4.15-4.08 (m, 2H, J5,6=4.5, J6a,6b=12.3 Hz, H-6aD, 6bD), 4.00 (m, 1H, H-2D), 3.90 (dd, 1H, J2,3=3.3, H-2A), 3.86 (dd, 1H, J3,4=9.5 Hz, H-3A), 3.85 (dq, 1H, J4,5=9.5, J5,6=6.2 Hz, H-5A), 3.50 (m, 1H, H-5D), 3.30 (pt, 1H, H-4A), 2.85 (d, 1H, J1,OH=3.5 Hz, OH), 2.02, 1.97, 1.94 (3s, 9H, OAc), 1.23 (d, 3H, H-6A); 13C NMR: δ 171.1, 170.0, 169.6, 162.1 (C═O), 138.5-127.1 (Ph), 101.7 (C-1D), 94.1 (C-1A), 92.6 (CCl3), 81.4 (C-4A), 79.9 (C-2A), 77.3 (C-3A), 75.9, 74.1 (2C, CH2Ph), 72.7 (C-3D), 72.5 (C-5D), 68.6 (C-4D), 68.4 (C-5A), 62.2 (C-6D), 56.1 (C-2D), 21.1, 21.0, 20.9 (3C, OAc), 18.3 (C-6A). FAB-MS for C34H40Cl3NO13 (M, 775), m/z 789 [M+Na]+. Anal. Calcd for C34H40Cl3NO13: C, 52.55; H, 5.19; N, 1.80%. Found: C, 52.48; H, 5.37; N, 1.67%.

出典