Methanesulfonyl chloride → (+/-)-(1S,2R,65)-2-((tert-butoxycarbonyl)amino)-6-methyl-4-(3-nitropyridin-4-yl)cyclohex-3-en-1-yl methanesulfonate

HRID 879193Notes

Reaction equation

HRID 879193 reaction equation
[OH:1][C@@H:2]1[C@H:7]([NH:8][C:9](=[O:15])[O:10][C:11]([CH3:14])([CH3:13])[CH3:12])[CH:6]=[C:5]([C:16]2[CH:21]=[CH:20][N:19]=[CH:18][C:17]=2[N+:22]([O-:24])=[O:23])[CH2:4][C@@H:3]1[CH3:25].[CH3:26][S:27](Cl)(=[O:29])=[O:28]>N1C=CC=CC=1>[CH3:26][S:27]([O:1][C@H:2]1[C@@H:3]([CH3:25])[CH2:4][C:5]([C:16]2[CH:21]=[CH:20][N:19]=[CH:18][C:17]=2[N+:22]([O-:24])=[O:23])=[CH:6][C@H:7]1[NH:8][C:9]([O:10][C:11]([CH3:12])([CH3:13])[CH3:14])=[O:15])(=[O:29])=[O:28]

Participants

4

Reactant 2

HCID 31297Methanesulfonyl chlorideHCID 86705242(+/-)-Tert-butyl (1R,5S,6S)-6-hydroxy-5-methyl-3-(3-nitropyridin-4-yl)cyclohex-2-enylcarbamate

Product 1

HCID 86705241(+/-)-(1S,2R,65)-2-((tert-butoxycarbonyl)amino)-6-methyl-4-(3-nitropyridin-4-yl)cyclohex-3-en-1-yl methanesulfonateYield 46%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Procedure

To a solution of (+/−)-tert-butyl ((1R,5S,6S)-6-hydroxy-5-methyl-3-(3-nitropyridin-4-yl)cyclohex-2-en-1-yl)carbamate (1.0 equiv.) in pyridine (0.20 M) was added MsCl (5.0 equiv.). The capped solution was stirred for 5 minutes and then the homogeneous solution was left standing at rt for 16 hrs. The volatiles were removed in vacuo and the residue was partitioned between EtOAc and H2O. The organic layer was washed with 10% CuSO4, H2O, Na2CO3(sat.), NaCl(sat.), dried over MgSO4, filtered, concentrated and purified by ISCO SiO2 chromatography to yield (+/−)-(1S,2R,6S)-2-((tert-butoxycarbonyl)amino)-6-methyl-4-(3-nitropyridin-4-yl)cyclohex-3-en-1-yl methanesulfonate in 46% yield. LC/MS (m/z)=428.2 (MH+), Rt=0.89 min.

Workup

  1. waitthe homogeneous solution was left
  2. waitstanding at rt for 16 hrs
  3. customThe volatiles were removed in vacuo
  4. customthe residue was partitioned between EtOAc and H2O
  5. washThe organic layer was washed with 10% CuSO4, H2O, Na2CO3(sat.), NaCl(sat.)
  6. dry with materialdried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. custompurified by ISCO SiO2 chromatography

Sources & evidence

ORD record
ord-ed30ecc2dfa14eb48b3e9c9807311fd9
Source dataset
uspto-grants-2015_03
Patent number
US08987457B2

Reaction notes

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