Lithium Hydroxide → (+/-)-Tert-butyl (1R,5S,6S)-6-hydroxy-5-methyl-3-(3-nitropyridin-4-yl)cyclohex-2-enylcarbamate

HRID 879204Notes

Reaction equation

[CH3:1][C@@H:2]1[C@H:10]2[C@H:6]([N:7]([C:12]([O:14][C:15]([CH3:18])([CH3:17])[CH3:16])=[O:13])C(=O)[O:9]2)[CH:5]=[C:4]([C:19]2[CH:24]=[CH:23][N:22]=[CH:21][C:20]=2[N+:25]([O-:27])=[O:26])[CH2:3]1.[Li+].[OH-]>C1COCC1.CCOC(C)=O.C([O-])(O)=O.[Na+]>[OH:9][C@@H:10]1[C@H:6]([NH:7][C:12](=[O:13])[O:14][C:15]([CH3:16])([CH3:17])[CH3:18])[CH:5]=[C:4]([C:19]2[CH:24]=[CH:23][N:22]=[CH:21][C:20]=2[N+:25]([O-:27])=[O:26])[CH2:3][C@@H:2]1[CH3:1]

Participants

Conditions

Temperature: 22 °C

Procedure

To a solution of (+/−)-(3aR,7S,7aS)-tert-butyl 7-methyl-5-(3-nitropyridin-4-yl)-2-oxo-3a,6,7,7a-tetrahydrobenzo[d]oxazole-3(2H)-carboxylate (1.0 equiv.) in THF (0.20 M) was added 2M LiOH (3.0 equiv.) was added. The mixture was stirred overnight 20 hrs at 22° C. The mixture was diluted with EtOAc and NaHCO3(aq.). The layers were separated and the aqueous was extracted with EtOAc. The combined organics were washed with brine, dried over Na2SO4, filtered, and concentrated. The golden foam was purified by ISCO chromatography to afford (+/−)-tert-butyl ((1R,5S,6S)-6-hydroxy-5-methyl-3-(3-nitropyridin-4-yl)cyclohex-2-en-1-yl)carbamate in 83% yield. LC/MS (m/z)=350.2 (MH+), Rt=0.82 min.

Workup

additionwas added
customThe layers were separated
extractionthe aqueous was extracted with EtOAc
washThe combined organics were washed with brine
dry with materialdried over Na2SO4
filtrationfiltered
concentrationconcentrated
customThe golden foam was purified by ISCO chromatography

Sources & evidence

ORD record: ord-ed732b141e714177bb3493f055ae31cf
Source dataset: uspto-grants-2015_03
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08987457B2

Reaction notes

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