Nitromethane → (2S,5S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-5-hydroxy-4-(2-nitroethyl)-5,6-dihydropyridine-1 (2H)-carboxylate

HRID 627231Notes

Reaction equation

HRID 627231 reaction equation
[Si:1]([O:8][CH2:9][C@@H:10]1[CH:15]=[C:14]([CH2:16]OC(OCC)=O)[C@H:13]([OH:23])[CH2:12][N:11]1[C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].[N+:31]([CH3:34])([O-:33])=[O:32]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[Si:1]([O:8][CH2:9][C@@H:10]1[CH:15]=[C:14]([CH2:16][CH2:34][N+:31]([O-:33])=[O:32])[C@H:13]([OH:23])[CH2:12][N:11]1[C:24]([O:26][C:27]([CH3:28])([CH3:30])[CH3:29])=[O:25])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

4

Reactant 2

HCID 6375NitromethaneHCID 89852382(2S,5S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-4-((ethoxycarbonyloxy)methyl)-5-hydroxy-5,6-dihydropyridine-1(2H)-carboxylate2×

Product 1

HCID 89852570(2S,5S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-5-hydroxy-4-(2-nitroethyl)-5,6-dihydropyridine-1 (2H)-carboxylate

Reagents, catalysts & solvents 1

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalyst

Procedure

(2S,5S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-4-((ethoxycarbonyloxy)methyl)-5-hydroxy-5,6-dihydropyridine-1(2H)-carboxylate (Intermediate 218, 14.5 g, 32.54 mmol) was taken up in nitromethane (100 ml, 1854.52 mmol) and degassed for 5 minutes. Pd2(dba)3 (1.49 g, 1.63 mmol) was added and the reaction mixture was stirred under nitrogen at room temperature for 18 hrs. Reaction mixture was dried directly onto silica and purified by flash chromatography using 0-50% EtOAc/Hexanes. The title compound was obtained as a yellow oil (6 g, 44.3%).

Workup

  1. customdegassed for 5 minutes
  2. customReaction mixture
  3. customwas dried directly onto silica
  4. custompurified by flash chromatography

Sources & evidence

ORD record
ord-a6b53bc724d84a3f8e0d13001a3affd8
Source dataset
uspto-grants-2016_04
Patent number
US09309245B2

Reaction notes

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