(2S,5R)-tert-butyl 5-(N-(allyloxy)-2,4-dinitrophenylsulfonamido)-2-((tert-butyldimethylsilyloxy)methyl)-5,6-dihydropyridine-1(2H)-carboxylate → N-(allyloxy)-N-((3R,6S)-6-((tert-butyldimethylsilyloxy)methyl)-1,2,3,6-tetrahydropyridin-3-yl)-2,4-dinitrobenzenesulfonamide

HRID 627157Notes

Reaction equation

HRID 627157 reaction equation
[CH2:1]([O:4][N:5]([C@H:21]1[CH2:26][N:25](C(OC(C)(C)C)=O)[C@H:24]([CH2:34][O:35][Si:36]([C:39]([CH3:42])([CH3:41])[CH3:40])([CH3:38])[CH3:37])[CH:23]=[CH:22]1)[S:6]([C:9]1[CH:14]=[CH:13][C:12]([N+:15]([O-:17])=[O:16])=[CH:11][C:10]=1[N+:18]([O-:20])=[O:19])(=[O:8])=[O:7])[CH:2]=[CH2:3]>C(Cl)Cl.[Br-].[Zn+2].[Br-]>[CH2:1]([O:4][N:5]([C@@H:21]1[CH:22]=[CH:23][C@@H:24]([CH2:34][O:35][Si:36]([C:39]([CH3:42])([CH3:41])[CH3:40])([CH3:37])[CH3:38])[NH:25][CH2:26]1)[S:6]([C:9]1[CH:14]=[CH:13][C:12]([N+:15]([O-:17])=[O:16])=[CH:11][C:10]=1[N+:18]([O-:20])=[O:19])(=[O:8])=[O:7])[CH:2]=[CH2:3]

Participants

4

Reactant 1

HCID 89852173(2S,5R)-tert-butyl 5-(N-(allyloxy)-2,4-dinitrophenylsulfonamido)-2-((tert-butyldimethylsilyloxy)methyl)-5,6-dihydropyridine-1(2H)-carboxylate2×

Product 1

HCID 89852376N-(allyloxy)-N-((3R,6S)-6-((tert-butyldimethylsilyloxy)methyl)-1,2,3,6-tetrahydropyridin-3-yl)-2,4-dinitrobenzenesulfonamideYield 106.7%

Reagents, catalysts & solvents 2

HCID 10421208Zinc bromideCatalystHCID 6344DichloromethaneSolvent2×

Procedure

To a stirred solution of (2S,5R)-tert-butyl 5-(N-(allyloxy)-2,4-dinitrophenylsulfonamido)-2-((tert-butyldimethylsilyloxy)methyl)-5,6-dihydropyridine-1(2H)-carboxylate (Intermediate 126, 19.5 g, 31.01 mmol) in DCM (250 mL) under nitrogen at rt, zinc bromide (20.95 g, 93.04 mmol) was added. The reaction mixture was stirred at rt for 6 hs, (lcms indicated the reaction was a clean one) and diluted with 50 mL DCM and washed with sat. NaHCO3, brine, dried over MgSO4, filtered and concentrated to give the desired product as an orange oil (17.5 g).

Workup

  1. washwashed with sat. NaHCO3, brine
  2. dry with materialdried over MgSO4
  3. filtrationfiltered
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-d870f3198aee46e19a6861356ce26ca4
Source dataset
uspto-grants-2016_04
Patent number
US09309245B2

Reaction notes

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