HCID 14077945, compound → HCID 67481674, compound

HRID 2273035Notes

Reaction equation

HRID 2273035 reaction equation
[N+:1]([CH:4]1[CH:19]([OH:20])[CH:8]2[O:9][CH:10]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)[O:11][CH2:12][CH:7]2[CH2:6][CH:5]1[OH:21])([O-])=O>CO.[NH4+].[OH-].[Ni]>[NH2:1][CH:4]1[CH:19]([OH:20])[CH:8]2[O:9][CH:10]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)[O:11][CH2:12][CH:7]2[CH2:6][CH:5]1[OH:21]

Participants

5

Reactant 1

HCID 14077945HCID 14077945, compound

Product 1

HCID 67481674HCID 67481674, compoundYield 81%

Reagents, catalysts & solvents 3

HCID 935NickelCatalystHCID 887MethanolSolventHCID 14923Ammonium HydroxideSolvent

Procedure

To a solution of rac-(2R,4aR,6R,7S,8R,8aR)-7-nitro-2-phenylhexahydro-4H-benzo[d][1,3]dioxine-6,8-diol (Carb. Res. 2002, 337, 1979-1992) (900 mg, 3.05 mmol) in MeOH (25 mL) and NH4OH (28% aqueous solution, 0.4 mL) was added Raney-Nickel (˜3 g). The mixture was hydrogenated at room temperature under atmosphere pressure for 20 h. The catalyst was filtered off and washed with MeOH. Solvents were evaporated to give the crude product. This was purified by silica gel chromatography, eluted with 15% MeOH in DCM and 83:14:3 DCM-MeOH-ammonia to give pure rac-(2R,4aR,6R,7S,8R,8aR)-7-amino-2-phenylhexahydro-4H-benzo[d][1,3]dioxine-6,8-diol (653 mg, 81%) as a white solid. 1H NMR (600 MHz, CD3OD) δ 7.52-7.50 (m, 2H), 7.37-7.32 (m, 3H), 5.58 (s, 1H), 4.13 (dd, J=11.0, 4.3, 1H), 3.68 (t, J=11.0, 1H), 3.51-3.41 (m, 3H), 2.67 (t, J=9.3, 1H), 1.83-1.76 (m, 2H), 1.17 (q, J=13.0, 1H).

Workup

  1. filtrationThe catalyst was filtered off
  2. washwashed with MeOH
  3. customSolvents were evaporated
  4. customto give the crude product
  5. customThis was purified by silica gel chromatography
  6. washeluted with 15% MeOH in DCM and 83:14:3 DCM-MeOH-ammonia

Sources & evidence

ORD record
ord-aefe3208ac784f8cb1375dbb36d45ba6
Source dataset
uspto-grants-2015_09
Patent number
US09120781B2

Reaction notes

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