HCID 14077945, compound → HCID 67481674, compound

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

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).