반응 #330935

반응 방정식

2,2,2-trichioroethoxycarbonyl chloride

dichloromethane

methanol

benzyl 2-amino-3,4,6-tri-O-benzyl-2-deoxy-β-D-glucopyranosyl-(1→4)-2-acetamido-3-O-allyl-6-O-benzyl-2-deoxy-α-D-glucopyranoside

dichloromethane pyridine

→

14

수율 74.0%

Benzyl 3,4,6-tri-O-benzyl-2-deoxy-2-[(2,2,2-trichloroethoxy)carbonyl]-amino-β-D-glucopyranosyl-(1→4)-2-acetamido-3-O-allyl-6-O-benzyl-2-deoxy-α-D-glucopyranoside

수율 74.0%

반응 조건

후처리

1. 1
   기타equipped with a septum at 0° C
2. 2
   온도The mixture was cooled to 0° C.
3. 3
   workup.WAITthe stirring was continued at room temperature for additional 2 h
4. 4
   기타Then the mixture was evaporated
5. 5
   workup.DISSOLUTIONthe residue was dissolved in dichloromethane (50 ml)
6. 6
   추출The solution was extracted with cold 5% aqueous sodium hydrogen sulfate (3×30 ml), cold saturated aqueous solution of sodium hydrogen carbonate (2×20 ml)
7. 7
   세척washed with brine (3×20 ml)
8. 8
   건조dried (MgSO4)
9. 9
   기타evaporated
10. 10
    기타Chromatography of the residue on a silica gel column (30 g) in chloroform-ethyl acetate (5:1) followed by crystallization from dichloromethane-n-heptane

실험 절차

To a stirred solution of benzyl 2-amino-3,4,6-tri-O-benzyl-2-deoxy-β-D-glucopyranosyl-(1→4)-2-acetamido-3-O-allyl-6-O-benzyl-2-deoxy-α-D-glucopyranoside 12 (ref.29; 873 mg, 1 mmol) and 4-dimethylaminopyridine (12 mg, 0.1 mmol) in a mixture of dry dichloromethane-pyridine (12:1; 26 ml) under argon in apparatus equipped with a septum at 0° C. 1M solution of 2,2,2-trichioroethoxycarbonyl chloride in dry dichloromethane (3 ml, 3 mmol) was slowly added through the septum and the mixture was stirred at the same temperature for 1 h and at room temperature for 12 h. The mixture was cooled to 0° C., methanol (2 ml, 50 mmol) was added and the stirring was continued at room temperature for additional 2 h. Then the mixture was evaporated and the residue was dissolved in dichloromethane (50 ml). The solution was extracted with cold 5% aqueous sodium hydrogen sulfate (3×30 ml), cold saturated aqueous solution of sodium hydrogen carbonate (2×20 ml), washed with brine (3×20 ml), dried (MgSO4) and evaporated. Chromatography of the residue on a silica gel column (30 g) in chloroform-ethyl acetate (5:1) followed by crystallization from dichloromethane-n-heptane afforded 776 mg (74%) of 14; m.p. 186-188° C., [α]D +36° (c 1.4, chloroform). IR (chloroform): 3443 (N—H, Ac); 3394 (N—H, Troc); 3089, 3067, 3033 (C—H, arom); 1749 (C═O, Troc); 1677 (amide I); 1648 (C═C); 1516 (amide II); 1607, 1587, 1497, 1454 (arom. ring). 1H NMR spectrum: 7.45-7.20 m, 25H (H-arom.); 5.77 dddd, 1H, J=4.8, 6.3, 10.4, 17.3 (CH2CH═CH2); 5.46 bd, 1H, J=9.1 (NHCOCH3); 5.14 dq, 1H, J=1.7, 1.7, 1.7, 17.3 (CH2CH═CH2); 4.99 ddt, 1H, J=1.3, 1.3, 2.1, 10.4 (CH2CH═CH2); 4.94 d, 1H, J=3.8 (H-1); 4.80 d, 1H, J=12.1 (CH2-Ph); 4.76 d, 1H, J=11.2 (CH2-Ph); 4.73 d, 1H, J=10.9 (CH2-Ph); 4.64 d, 1H, J=11.9 (CH2-Ph); 4.64 d, 1H, J=11.5 (CH2-Ph); 4.60 d, 1H, J=11.2 (CH2-Ph); 4.58 d, 1H, J=11.5 (CH2-Ph); 4.57 d, 1H, J=10.9 (CH2-Ph); 4.56 d, 1H, J=12.0 (CO2CH2CCl3); 4.50 d, 1H, J=12.0 (CO2CH2CCl3); 4.44 d, 1H, J=11.9 (CH2-Ph); 4.42 ddt, 1H, J=1.6, 1.6, 4.8, 13.4 (CH2CH═CH2); 4.35 d, 1H, J=12.1 (CH2-Ph); 4.20 bd, 1H, J=8.1 (H-1′); 4.19 ddd, 1H, J=3.8, 9.1, 10.6 (H-2); 3.99 bd, 1H, J=10.0 (NHCO2CH2CCl3); 3.93 ddt, 1H, J=1.4, 1.4,6.3, 13.4 (CH2CH═CH2); 3.87 dd, 1H, J=8.8, 9.8 (H-4); 3.74 dd, 1H, J=2.4, 10.8 (H-6a′); 3.73 dd, 1H, J=3.4, 10.6 (H-6a); 3.70 dd, 1H, J=3.7, 10.8 (H-6b′); 3.66 ddd, 1H, J=2.4, 3.4, 9.8 (H-5); 3.66 dd, 1H, J=8.8, 9.8 (H-4′); 3.50-3.42 m, 1H (H-6b); 3.50-3.42 m, 1H (H-3); 3.50-3.42 m, 1H (H-2′); 3.27 bdt, 1H, J=2.9, 2.9, 9.8 (H-5′); 3.23 bt, 1H, J=9.6, 9.6 (H-3′); 1.93 s, 3H (NHCOCH3). 13C NMR spektrum: 173.11 (CO2CH2CCl3); 169.59 (COCH3); 138.62; 138.23; 138.16; 137.91; 137.14; 135.90 (CH2CH═CH2); 129.22; 128.89; 128.56 (2C); 128.40 (3C); 128.39 (3C); 128.33 (3C); 128.10; 128.07 (3C); 127.89 (2C); 127.76; 127.70; 127.64 (2C); 127.59; 127.49; 115.87 (CH2CH═CH2); 100.76 (C′-1); 97.05 (C-1); 95.66 (CO2CH2CCl3); 82.11 (C′-3); 78.52 (C-3); 78.28 (C′-4); 77.19 (C-4); 74.80 (CH2-Ph); 74.73 (CO2CH2CCl3); 74.71 (C′-5); 74.52 (CH2-Ph); 73.61 (CH2-Ph); 73.46 (CH2-Ph); 73.37 (CH2CH═CH2); 70.57 (C-5); 69.89 (CH2-Ph); 68.71 (C-6); 67.79 (C′-6); 57.89 (C′-2); 52.33 (C-2); 23.34 (COCH3).

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