Acetic Acid → (2S,3R,4R) 3,4-dihydroxypipecolic acid, monohydrate

HRID 2050674Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 2050674
C([O:8][C@H:9]1[C@H:14]2[CH2:15][CH2:16][N:17](C(OCC3C=CC=CC=3)=O)[C@@H:10]1[C:11]([O:13]2)=[O:12])C1C=CC=CC=1.C(O)(=[O:30])C>O.[Pd]>[OH2:8].[OH:8][C@H:9]1[C@H:14]([OH:13])[CH2:15][CH2:16][NH:17][C@@H:10]1[C:11]([OH:12])=[O:30]

Komponenten

5

Edukt 2

HCID 176Acetic AcidHCID 145234483-O-benzyl-N-benzyloxycarbonyl-2,6-imino-2,5,6-trideoxy-D-lyxo-hexono-1,4-lactone

Produkt 1

HCID 131716888(2S,3R,4R) 3,4-dihydroxypipecolic acid, monohydrateAusbeute 89 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 23938PalladiumKatalysatorHCID 962WaterLösungsmittel

Versuchsvorschrift

3-O-Benzyl-N-benzyloxycarbonyl-2,6-imino-2,5,6-trideoxy-D-lyxo-hexono-1,4-lactone (26) (321 mg, 0.875 mmol) was dissolved in a 2:1 mixture of acetic acid and water (10 ml) and stirred under hydrogen with palladium black (70 mg) for 48 hours. The reaction mixture was filtered through celite, the solvent removed and the product purified by flash chromatography (CMAW) and ion exchange chromatography. Freeze drying afforded (2S,3R,4R) 3,4-dihydroxypipecolic acid, monohydrate (140 mg, 89%) as a white crystalline solid, m.p. 253°-260° C. with decomposition, [α]20D -1.3° (c, 0.54 in water); νmax (KBr disc) 3390, 1595 (CO), 1400, 1080, 1060 and 890 cm-1 ; 1H NMR (D2O) δ 1.48-1.61 (1H, m, 5-H); 1.99 (1H, ddt, H-5', J5,5' 14.4 Hz, J5', 6;5',6';5',4 3.7 Hz); 2.88 (1H, ddd, 6-H, J6,6' 13.0 Hz, J5,6 11.9 Hz); 3.26 (1H, dt, H-6', J5,6' 3.7 Hz); 3.30 (1H, d, 2-H, J2,3 9.2 Hz); 3.52-3.61 (2H, m, H-3, H-4); 13C NMR (D2O) δ 28.33 (t, C-2); 41.13 (t, C-1); 61.51 (d, H-5); 70.24, 71.85 (2×d, C-3,4); 172.43 (s, C-1). m/z: 124 (M-2×H2O-H+, 100%), 98 (M-H2O-CO2H+, 95%), 116 (M-CO2H+, 75%), 162 (M+H+, 67%). (Found C, 40.16; H, 7.10; N, 7.56. C6H11NO4.H2O requires C, 40.22; H, 7.31; N, 7.82).

Aufarbeitung

  1. filtrationThe reaction mixture was filtered through celite
  2. customthe solvent removed
  3. customthe product purified by flash chromatography (CMAW) and ion exchange chromatography
  4. customFreeze drying

Quellen und Nachweise

ORD-Eintrag
ord-0025e1aef0a64836aeb64dcf19b0c65a
Quelldatensatz
uspto-grants-1991_05
Patentnummer
US05013842

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