Acetic Acid → N-Benzhydryl-1-deoxynojirimycin

HRID 486305Notes

Reaction equation

HRID 486305 reaction equation
[CH2:1]([OH:12])[C:2]([C@@H:4]([OH:11])[C@H:5]([OH:10])[C@@H:6]([OH:9])[CH:7]=O)=O.[CH:13]([NH2:26])([C:20]1[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1)[C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.C(O)(=O)C.C([BH3-])#N.[Na+]>CO>[CH2:7]1[N:26]([CH:13]([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[C@H:2]([CH2:1][OH:12])[C@@H:4]([OH:11])[C@H:5]([OH:10])[C@H:6]1[OH:9]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 7036BenzhydrylamineHCID 5003444Sodium cyanoborohydrideHCID 11137679HCID 11137679, compound

Product 1

HCID 11099542N-Benzhydryl-1-deoxynojirimycinYield 69%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a -78° C. solution of 5-keto-D-glucose (Formula V, 4.00 g, 0.0225 mol) in 100 mL of methanol was added a cooled solution (-78° C.) of benzhydrylamine (3.29 g, 0.018 mol) and acetic acid (1.08 g, 0.018 mol) in 100 mL of methanol. Sodium cyanoborohydride (2.82 g, 0.0449 mole) was added, and the mixture was stirred at -78° C. for 2 h and then slowly warmed to ambient temperature. After 18 h, the solution was concentrated, saturated aqueous sodium carbonate was added, and the product was extracted into chloroform. The chloroform extracts were combined, dried (sodium sulfate), and concentrated to afford a yellow foam. Chromatographic purification on flash silica gel (5-10% gradient of methanol in chloroform) afforded 4.06 g (69%) of the title compound as a very pale yellow foam. 1H NMR and reversed-phase analytical HPLC showed that this substance was >95% stereochemically pure (ca. 4.5% of the iditol isomer). Recrystallization from MEOH afforded white needles, mp 101°-104° C. (corrected). Both 1H and 13C NMR in CDCl3 and D3CC(O)CD3 confirmed the structure.

Workup

  1. temperatureslowly warmed to ambient temperature
  2. waitAfter 18 h
  3. concentrationthe solution was concentrated
  4. additionsaturated aqueous sodium carbonate was added
  5. extractionthe product was extracted into chloroform
  6. dry with materialdried (sodium sulfate)
  7. concentrationconcentrated
  8. customto afford a yellow foam
  9. customChromatographic purification on flash silica gel (5-10% gradient of methanol in chloroform)

Sources & evidence

ORD record
ord-51a12ea5de804c52947b3405c04c1a5d
Source dataset
uspto-grants-1994_03
Patent number
US05290948

Reaction notes

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