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

HRID 2050672

反応式

HRID 2050672 の反応式
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

参加物

4

反応物 1

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

生成物 1

HCID 72259Fagomine

試薬・触媒・溶媒 2

HCID 23938Palladium触媒HCID 176Acetic Acid溶媒

実験手順

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).

後処理

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

出典と根拠

ORDレコード
ord-4bbf98bb34f54aaab887dbf992bf9c28
出典データセット
uspto-grants-1991_05
特許番号
US05013842

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