2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → (2S)-tert-butyl 5-(N-(allyloxy)-2-nitrophenylsulfonamido)-2-(((tert-butyldimethylsilyl)oxy)methyl)-4-(hydroxymethyl)-5,6-dihydropyridine-1(2H)-carboxylate

HRID 627192Notes

Reaction equation

HRID 627192 reaction equation
[CH2:1]([O:4][N:5]([CH:18]1[CH2:23][N:22]([C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])[C@H:21]([CH2:31][O:32][Si:33]([C:36]([CH3:39])([CH3:38])[CH3:37])([CH3:35])[CH3:34])[CH:20]=[C:19]1[CH2:40][O:41]CC1C=CC(OC)=CC=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].C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>C(Cl)Cl.O>[CH2:1]([O:4][N:5]([CH:18]1[CH2:23][N:22]([C:24]([O:26][C:27]([CH3:29])([CH3:30])[CH3:28])=[O:25])[C@H:21]([CH2:31][O:32][Si:33]([C:36]([CH3:39])([CH3:38])[CH3:37])([CH3:35])[CH3:34])[CH:20]=[C:19]1[CH2:40][OH:41])[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]

Participants

4

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 89851796(2S)-tert-butyl 5-(N-(allyloxy)-2-nitrophenylsulfonamido)-2-(((tert-butyldimethylsilyl)-oxy)methyl)-4-(((4-methoxybenzyl)oxy)methyl)-5,6-dihydropyridine-1(2H)-carboxylate2×

Product 1

HCID 131735287(2S)-tert-butyl 5-(N-(allyloxy)-2-nitrophenylsulfonamido)-2-(((tert-butyldimethylsilyl)oxy)methyl)-4-(hydroxymethyl)-5,6-dihydropyridine-1(2H)-carboxylate

Reagents, catalysts & solvents 1

HCID 21908982Water methylene chlorideSolvent

Procedure

To a stirred solution of (2S)-tert-butyl 5-(N-(allyloxy)-2-nitrophenylsulfonamido)-2-(((tert-butyldimethylsilyl)oxy)methyl)-4-(((4-methoxybenzyl)oxy)methyl)-5,6-dihydropyridine-1(2H)-carboxylate (Intermediate 170, 18.70 g, 25.48 mmol) in DCM/water (180 mL/20 mL), was added DDQ (6.94 g, 30.57 mmol) at 0° C. The mixture was stirred at room temperature for 1 hour before it was concentrated. The residue was purified on silica gel column eluting with 0-100% ethyl acetate/hexanes to give a pale yellow oil, 12.38 g, 79%.

Workup

  1. concentrationwas concentrated
  2. customThe residue was purified on silica gel column
  3. washeluting with 0-100% ethyl acetate/hexanes
  4. customto give a pale yellow oil, 12.38 g, 79%

Sources & evidence

ORD record
ord-4216b817e7d647bf9406fe04dd24477f
Source dataset
uspto-grants-2016_04
Patent number
US09309245B2

Reaction notes

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