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

HRID 2050674Notes

Reaction equation

HRID 2050674 reaction equation
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]

Participants

5

Reactant 2

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

Product 1

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

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 962WaterSolvent

Procedure

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).

Workup

  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

Sources & evidence

ORD record
ord-0025e1aef0a64836aeb64dcf19b0c65a
Source dataset
uspto-grants-1991_05
Patent number
US05013842

Reaction notes

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