Water → HCID 57152591, compound

HRID 2050666Notes

Reaction equation

HRID 2050666 reaction equation
C(O[C@H:9]1[C@H:15]([OH:16])[CH2:14][N:13]([C:17]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)=[O:18])[C@@H:10]1[CH:11]=[O:12])C1C=CC=CC=1.[OH2:27].C(=O)([O-])[O-].[Ba+2].BrBr>O1CCOCC1>[CH2:20]([C@H:9]1[C@@H:15]([OH:16])[CH2:14][N:13]([C:17]([O:19][CH2:20][C:21]2[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=2)=[O:18])[C@@H:10]1[C:11]([OH:12])=[O:27])[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1

Participants

6

Reactant 4

HCID 962WaterHCID 10563Barium CarbonateHCID 24408Bromine2×HCID 14523424HCID 14523424, compound

Product 1

HCID 57152591HCID 57152591, compoundYield 75%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 3-O-benzyl-N-benzyloxycarbonyl-2,5-dideoxy-2,5-imino-D-lyxose (15) (900 mg, 2.54 mmol), in a 1:1 mixture of water and 1,4-dioxan (15 ml) containing barium carbonate (1.46 g, 7.62 mmol), was cooled to 0° C. and treated with bromine (298 μl, 5.33 mmol). After stirring for 24 hours excess bromine was destroyed by the dropwise addition of 10% sodium thiosulphate solution and the suspension acidified with 2M HCl (20 ml). The product was extracted into dichloromethane (4×50 ml), dried, filtered and evaporated. Purification by flash chromatography (ethyl acetate-hexane (1:1 to ethyl acetate) afforded (2S,3R,4R)-3-benzyl-N-benzyloxycarbonyl-4-hydroxyproline (738 mg, 75%) as a clear oil, [α]20D -3.7° (c, 0.88 in chloroform); νmax (film) 3400 (OH), 2950, 1680 (2×CO), 1425, 1360 and 1195 cm-1 ; 1H NMR δ 3.62-3.78 (2H, 2×dd, H-5); 4.21, 4.26 (2H, s, and bs, H-3, H-2); 4.49-4.69 (3H, m, CH2Ph); 5.06-5.18 (2H, 2×dd, CH2 -Z); 5.6 (2H, bs, 2×OH); 7.27-7.38 (10H, m, 2×H-Ph). m/z: 91 (100%), 310 (45%), 372 (M+H+, 30%).

Workup

  1. customwas destroyed by the dropwise addition of 10% sodium thiosulphate solution
  2. extractionThe product was extracted into dichloromethane (4×50 ml)
  3. customdried
  4. filtrationfiltered
  5. customevaporated
  6. customPurification by flash chromatography (ethyl acetate-hexane (1:1 to ethyl acetate)

Sources & evidence

ORD record
ord-41a135113bb940e8bb149f8e7013f169
Source dataset
uspto-grants-1991_05
Patent number
US05013842

Reaction notes

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