Thioglycolic Acid → (3R,6S)-6-[[(tert-butyldimethylsilyl)oxy]methyl]-5-methyl-N-(prop-2-en-1-yloxy)-1,2,3,6-tetrahydropyridin-3-amine

HRID 627172Notes

Reaction equation

HRID 627172 reaction equation
[Si:1]([O:8][CH2:9][C@H:10]1[NH:15][CH2:14][C@H:13]([N:16]([O:29][CH2:30][CH:31]=[CH2:32])S(C2C=CC=CC=2[N+]([O-])=O)(=O)=O)[CH:12]=[C:11]1[CH3:33])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].SCC(O)=O.[Li+].[OH-]>CN(C)C=O.O>[Si:1]([O:8][CH2:9][C@H:10]1[NH:15][CH2:14][C@H:13]([NH:16][O:29][CH2:30][CH:31]=[CH2:32])[CH:12]=[C:11]1[CH3:33])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:2])[CH3:3]

Participants

6

Reactant 3

HCID 1133Thioglycolic AcidHCID 3939Lithium HydroxideHCID 89852660N-[(3R,6S)-6-[[(tert-butyldimethylsilyl)oxy]methyl]-5-methyl-1,2,3,6-tetrahydropyridin-3-yl]-2-nitro-N-(prop-2-en-1-yloxy)benzene-1-sulfonamide2×

Product 1

HCID 89852532(3R,6S)-6-[[(tert-butyldimethylsilyl)oxy]methyl]-5-methyl-N-(prop-2-en-1-yloxy)-1,2,3,6-tetrahydropyridin-3-amine

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

Into a 250-mL round-bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed a solution of N-[(3R,6S)-6-[[(tert-butyldimethylsilyl)oxy]methyl]-5-methyl-1,2,3,6-tetrahydropyridin-3-yl]-2-nitro-N-(prop-2-en-1-yloxy)benzene-1-sulfonamide (Intermediate 146, 12 g, 24.11 mmol, 1.00 equiv) in N,N-dimethylformamide (100 mL), 2-sulfanylacetic acid (4.4 g, 47.77 mmol, 2.00 equiv). This was followed by the addition of LiOH (5.8 g, 242.17 mmol, 10.00 equiv), in portions. The resulting solution was stirred for 2 h at room temperature. The resulting solution was diluted with 500 mL of water. The resulting solution was extracted with 5×200 mL of ethyl acetate and the organic layers combined. The resulting mixture was washed with 3×200 mL of brine and 2×200 mL of sodium bicarbonate (aq.). The mixture was dried over anhydrous sodium sulfate and concentrated under vacuum. This resulted in 8.4 g (crude product) of the title compound as yellow oil.

Workup

  1. customInto a 250-mL round-bottom flask purged
  2. temperaturemaintained with an inert atmosphere of nitrogen
  3. extractionThe resulting solution was extracted with 5×200 mL of ethyl acetate
  4. washThe resulting mixture was washed with 3×200 mL of brine and 2×200 mL of sodium bicarbonate (aq.)
  5. dry with materialThe mixture was dried over anhydrous sodium sulfate
  6. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-3ce0a04f97ac4ceb87e50cf37900a7b8
Source dataset
uspto-grants-2016_04
Patent number
US09309245B2

Reaction notes

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