Boron tribromide → (S)-5-amino-2'-bromo-4'-fluoro-2,6-dihydrospiro[[1,4]oxazine-3,9'-xanthen]-7'-ol
Reaction equation
[Br:1][C:2]1[CH:15]=[C:14]([F:16])[C:13]2[O:12][C:11]3[C:6](=[CH:7][C:8]([O:17]C)=[CH:9][CH:10]=3)[C@:5]3([N:23]=[C:22]([NH2:24])[CH2:21][O:20][CH2:19]3)[C:4]=2[CH:3]=1.BrB(Br)Br>C(Cl)Cl>[NH2:24][C:22]1[CH2:21][O:20][CH2:19][C@:5]2([C:4]3[CH:3]=[C:2]([Br:1])[CH:15]=[C:14]([F:16])[C:13]=3[O:12][C:11]3[C:6]2=[CH:7][C:8]([OH:17])=[CH:9][CH:10]=3)[N:23]=1Participants
4
Reactant 2
Product 1
Reagents, catalysts & solvents 1
Conditions
- Temperature
- 0 °C
Procedure
In a 500-mL flask, the (S)-2′-bromo-4′-fluoro-7′-methoxy-2,6-dihydrospiro[[1,4]oxazine-3,9′-xanthen]-5-amine (0.676 g, 1.719 mmol) was suspended in dcm (50 mL). The suspension was cooled to 0° C., and a DCM solution of tribromoborane (1.0 M, 5.16 mL, 5.16 mmol) was added. After 1.5 h, the reaction was quenched with 9:1 aqueous NH4Cl/NH4OH (20 mL). The aqueous phase was extracted with 5% MeOH/DCM (3×50 mL). The organics were combined, washed with brine (15 mL), dried over sodium sulfate and concentrated to afford crude (S)-5-amino-2′-bromo-4′-fluoro-2,6-dihydrospiro[[1,4]oxazine-3,9′-xanthen]-7′-ol (604 mg, 1.593 mmol) which was used directly in the next step.
Workup
- customthe reaction was quenched with 9:1 aqueous NH4Cl/NH4OH (20 mL)
- extractionThe aqueous phase was extracted with 5% MeOH/DCM (3×50 mL)
- washwashed with brine (15 mL)
- dry with materialdried over sodium sulfate
- concentrationconcentrated
Sources & evidence
- ORD record
- ord-dd2f735cfbf44619877c4b5cdc7029b9
- Source dataset
- uspto-grants-2013_07
- Patent number
- US08497264B2
Reaction notes
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