Ammonia → (3R,4R,5R)-3-Benzyloxy-5-hydroxymethyl4-piperidinol

HRID 343760Notes

Reaction equation

HRID 343760 reaction equation
[CH2:1]([O:8][C@H:9]([CH:17]=O)[C@H:10]([OH:16])[C@@H:11]([CH2:14][OH:15])[CH:12]=O)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.OCC1(OC[C@@H](O)[C@@H](O)[C@H]1O)O.[NH3:31]>C(O)C.[Pd]>[CH2:1]([O:8][C@H:9]1[C@H:10]([OH:16])[C@@H:11]([CH2:14][OH:15])[CH2:12][NH:31][CH2:17]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 222AmmoniaHCID 441036D-PsicoseHCID 152354804-O-Benzyl-2-deoxy-2-C-hydroxymethyl-D-xylo-pentodialdose

Product 1

HCID 15235481(3R,4R,5R)-3-Benzyloxy-5-hydroxymethyl4-piperidinolYield 78%

Reagents, catalysts & solvents 2

HCID 23938PalladiumCatalystHCID 702EthanolSolvent2×

Procedure

To a solution of 4-O-benzyl-2-deoxy-2-C-hydroxymethyl-D-xylo-pentodialdose (1.77 g) in ethanol (40 ml), 0.29M NH3 in ethanol (162 ml) and 5% palladium on charcoal (300 mg) was added. The mixture was hydrogenated at 500 Psi at 20° C. for 15 hours. The reaction mixture was filtrated and concentrated. The residue (1.85 g) was flash chromatographed using ethanol/NH4OH (25% aqueous)/trimethylamine (122:2:1) as eluent giving the product as a colourless sirup (getting coloured after storing) in 78% yield. 13C-NMR (62.9 MHz, D2O): δ138.1, 128.1, 127.3 (Ph); 80.6 (C-3), 74.9 (C-4); 71.8 (OCH2Ph); 62.5 (C-5'); 48.0 (C-2); 46.8 (C-6); 45.0 ppm (C-5). 1H-NMR (500 MHz, D2O): δ7.3 (s, 5H, Ph); 4.65, 4.51 (2 d, 2H, OCH2Ph, Jgem =12 Hz); 3.66 (dd, 1H, H-5a', J5a',5b' =10 Hz, J5',5 =5.5); 3.57 (dd, 1H, H-5'b, J5a', 5b'=10 Hz, J5b',5 =4.5); 3.41 (dd, 1H, H-4, J3,4 =11 Hz, J4,5 =9 Hz); 3.3 (broad, N--H); 3.27 (dd, 1H, H-3, J3,2zx =11 Hz, J3,2eq =4 Hz); 3.22 (dd, 1H, H-2eq, J2eq,2ax =11, J2eq,3 =4 Hz); 2.97 (dd, 1H, H-6 eq, J6eq,6ax =12 Hz, J6eq,5 =4 Hz); 2.38 (t, 1H, H-2ax, J2ax,2eq =J2ax,3=11 Hz); 2.31 (t, 1H, H-6ax, J6ax,6eq=J6ax,5 =12 Hz); 1.80 ppm (m, 1H, H-5).

Workup

  1. filtrationThe reaction mixture was filtrated
  2. concentrationconcentrated
  3. customchromatographed
  4. customgiving the product as a colourless sirup (getting coloured after storing) in 78% yield

Sources & evidence

ORD record
ord-5f055e597d3a4c4d8eef27ea39c02d11
Source dataset
uspto-grants-1999_01
Patent number
US05863903

Reaction notes

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