Hydrochloric Acid → (3R,4S)-3-(benzyloxy)tetrahydro-2H-pyran-4-amine

HRID 82439

Reaction equation

HRID 82439 reaction equation
[NH2:1][C@H](C(O)=O)C.C([O-])=O.[Na+].OP([O-])([O-])=O.[Na+].[Na+].C1N=C(N)C2N=CN([C@@H]3O[C@H](COP(OP(OC[C@H]4O[C@@H](N5C=C(C(N)=O)CC=C5)[C@H](O)[C@@H]4O)(O)=O)(O)=O)[C@@H](O)[C@H]3O)C=2N=1.CC1C(O)=C(C=O)C(COP(O)(O)=O)=CN=1.[CH2:78]([O:85][C@@H:86]1[C:91](=O)[CH2:90][CH2:89][O:88][CH2:87]1)[C:79]1[CH:84]=[CH:83][CH:82]=[CH:81][CH:80]=1.Cl.C(=O)([O-])[O-].[K+].[K+]>O.C(OCC)(=O)C>[CH2:78]([O:85][C@@H:86]1[C@@H:91]([NH2:1])[CH2:90][CH2:89][O:88][CH2:87]1)[C:79]1[CH:84]=[CH:83][CH:82]=[CH:81][CH:80]=1

Participants

11

Reactant 8

HCID 313Hydrochloric AcidHCID 1051Pyridoxal 5'-phosphateHCID 5950L-AlanineHCID 11430Potassium CarbonateHCID 24203Sodium Phosphate, DibasicHCID 439153NadhHCID 2723810Sodium FormateHCID 60209906(3S)-3-(benzyloxy)tetrahydro-4H-pyran-4-one

Product 1

HCID 60209907(3R,4S)-3-(benzyloxy)tetrahydro-2H-pyran-4-amine

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of L-Alanine (200 g, 2.24 mol), sodium formate (76.0 g, 1.12 mmol), and sodium phosphate dibasic (28.7 g, 202 mmol) in 2.25 L of water adjusted to pH 7.5 was added NAD (2.2 g, 3.21 mmol), pyridoxal-5-phosphate (2.2 g, 8.90 mmol), LDH (0.45 g, 0.22 mol), FDH (4.5 g, 0.20 mol), and TA P1 G5 (4.5 g, 0.22 mol). After all the components were completely dissolved, (3S)-3-(benzyloxy)tetrahydro-4H-pyran-4-one (45 g, 0.22 mol) was added and the pH was adjusted to pH 7.25 with 6 N HCl and aged at 30° C. After 15 h, potassium carbonate (700 g, 5.06 mol) was added slowly, followed by ethyl acetate (2.2 L). The mixture was filtered through a bed of Solka Floc and the cake was washed with ethyl acetate (250 mL). The combined filtrates were separated and the aqueous layer was extracted a second time with ethyl acetate (2 L). The combined organic extracts were concentrated in vacuo to provide crude (3R,4S)-3-(benzyloxy)tetrahydro-2H-pyran-4-amine.

Workup

  1. dissolutionAfter all the components were completely dissolved
  2. customaged at 30° C
  3. filtrationThe mixture was filtered through a bed of Solka Floc
  4. washthe cake was washed with ethyl acetate (250 mL)
  5. customThe combined filtrates were separated
  6. extractionthe aqueous layer was extracted a second time with ethyl acetate (2 L)
  7. concentrationThe combined organic extracts were concentrated in vacuo

Sources & evidence

ORD record
ord-07225e619eb640e285f6fccc978913dc
Source dataset
uspto-grants-2014_09
Patent number
US08846702B2

Linked notes

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