4-O-benzyl-N-benzyloxycarbonyl-1,5-imino-1,2,5-trideoxy-D-arabino-hexitol → Fagomine

HRID 2050672

반응식

HRID 2050672 반응식
C([O:8][C@@H:9]1[C@@H:14]([CH2:15][OH:16])[N:13](C(OCC2C=CC=CC=2)=O)[CH2:12][CH2:11][C@H:10]1[OH:27])C1C=CC=CC=1>C(O)(=O)C.[Pd]>[NH:13]1[C@H:14]([CH2:15][OH:16])[C@@H:9]([OH:8])[C@H:10]([OH:27])[CH2:11][CH2:12]1

참가 물질

4

반응물 1

HCID 145234464-O-benzyl-N-benzyloxycarbonyl-1,5-imino-1,2,5-trideoxy-D-arabino-hexitol

생성물 1

HCID 72259Fagomine

시약·촉매·용매 2

HCID 23938Palladium촉매HCID 176Acetic Acid용매

실험 절차

4-O-Benzyl-N-benzyloxycarbonyl-1,5-imino-1,2,5-trideoxy-D-arabino-hexitol (25) (325 mg, 0.877 mmol) was dissolved in acetic acid (8 ml) and stirred under hydrogen at atmospheric pressure with palladium black (100 mg). After 18 hours, the solution was filtered and evaporated. Subsequent purification by flash chromatography (CMAW) and ion exchange gave 1,5-imino-1,2,5-trideoxy-D-arabino-hexitol as the hydrochloride salt (158 mg, 98%) a white crystalline solid, m.p. (methanol-ether) 173°-175° C., [α]20D +17.9° (c, 0.78 in water); νmax (KBr disc) 3370, 1615, 1390, 1055, 935 and 660 cm-1 ; 1H NMR (D2O) δ 1.58 (1H, dddd, H-2, J2,2' 14.2 Hz, J2,3 11.4 Hz, J2,1 13.6 Hz, J2,1' 4.6 Hz); 2.06 (1H, dddd, J2',1' 2.4 Hz, J2',3 4.8 Hz, J2',1 3.2 Hz); 2.90-3.01 (2H, m, H-5, H-1); 3.30 (1H, ddd, H-1', J1,1' 13.2 Hz); 3.38 (1H, dd, H-4, J3,4 9.2 Hz, J4,5 10.5 Hz); 3.57 (1H, ddd, H-3); 3.73, 3.79 (2H, 2×dd, H-6,6', J6,6' 12.7 Hz, J5,6 5.2 Hz, J5,6' 3.4 Hz). 13C NMR δ29.33 (t, C-2); 42.66 (t, C-1); 58.53 (t, C-6); 60.68 (d, C-5); 70.39, 71.24 (2×d, C-3, C-4). m/z: 148 (M+H+, 100%), 116 (10%), 72 (8%). Also characterized as free base, m.p. (acetone-water) 178°-180° C., [lit.20 180°-184° C.], [α]20D +21.0° (c 0.3 in water) [lit.20 +24.7 (c 0.4 in water)]; 1H NMR δ 1.28 (1H, dddd, H-2), 1.81 (1H, dddd, H-2'), 2.40 (1H, ddd, H-1), 2.83 (1 H, ddd, H-1'), 2.99 (1H, dd, H-4), 3.37 (1H, m, H-3), 3.46 (1H, dd, H-6), 3.68 (1H, dd, H-6'); 13C NMR δ 33.45 (t, C-2), 43.30 (t, C-1), 61.59 (d, C-5), 62.45 (t, C-6), 73.98 (2×d, C-3,4).

후처리

  1. filtrationthe solution was filtered
  2. customevaporated
  3. customSubsequent purification by flash chromatography (CMAW) and ion exchange

출처 및 근거

ORD 기록
ord-4bbf98bb34f54aaab887dbf992bf9c28
출처 데이터셋
uspto-grants-1991_05
특허 번호
US05013842

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