(2S,5R)-tert-butyl 5-(N-(allyloxy)-2-nitrophenylsulfonamido)-2-((tert-butyldimethylsilyloxy)methyl)-3-methyl-5,6-dihydropyridine-1(2H)-carboxylate → 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

HRID 627171Notes

Reaction equation

HRID 627171 reaction equation
[CH2:1]([O:4][N:5]([C@H:18]1[CH2:23][N:22](C(OC(C)(C)C)=O)[C@H:21]([CH2:31][O:32][Si:33]([C:36]([CH3:39])([CH3:38])[CH3:37])([CH3:35])[CH3:34])[C:20]([CH3:40])=[CH:19]1)[S:6]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[N+:15]([O-:17])=[O:16])(=[O:8])=[O:7])[CH:2]=[CH2:3]>ClCCl.[Zn+2].[Br-].[Br-]>[Si:33]([O:32][CH2:31][C@H:21]1[NH:22][CH2:23][C@H:18]([N:5]([O:4][CH2:1][CH:2]=[CH2:3])[S:6]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=2[N+:15]([O-:17])=[O:16])(=[O:8])=[O:7])[CH:19]=[C:20]1[CH3:40])([C:36]([CH3:39])([CH3:38])[CH3:37])([CH3:35])[CH3:34]

Participants

4

Reactant 1

HCID 89852556(2S,5R)-tert-butyl 5-(N-(allyloxy)-2-nitrophenylsulfonamido)-2-((tert-butyldimethylsilyloxy)methyl)-3-methyl-5,6-dihydropyridine-1(2H)-carboxylate2×

Product 1

HCID 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-sulfonamide

Reagents, catalysts & solvents 2

HCID 10421208Zinc bromideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

Into a 250-mL round-bottom flask purged and maintained with an inert atmosphere of nitrogen, was placed a solution of tert-butyl (3R,6S)-6-[[(tert-butyldimethylsilyl)oxy]methyl]-5-methyl-3-[N-(prop-2-en-1-yloxy)(2-nitrobenzene)sulfonamido]-1,2,3,6-tetrahydropyridine-1-carboxylate (Intermediate 80, 13.6 g, 22.75 mmol, 1.00 equiv) in dichloromethane (100 mL). This was followed by the addition of ZnBr2 (10.2 g, 45.29 mmol, 2.00 equiv) in several batches. The resulting solution was stirred overnight at room temperature. The resulting solution was diluted with 500 mL of dichloromethane. The resulting mixture was washed with 2×200 mL of sodium bicarbonate (aq) and 2×200 mL of NH4Cl (aq). The mixture was dried over anhydrous sodium sulfate and concentrated under vacuum. This resulted in 12 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. washThe resulting mixture was washed with 2×200 mL of sodium bicarbonate (aq) and 2×200 mL of NH4Cl (aq)
  4. dry with materialThe mixture was dried over anhydrous sodium sulfate
  5. concentrationconcentrated under vacuum

Sources & evidence

ORD record
ord-0781c6d777d4402bb9ad8aec43ab6be2
Source dataset
uspto-grants-2016_04
Patent number
US09309245B2

Reaction notes

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