Iodine → (S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-4-iodo-5-oxo-5,6-dihydropyridine-1 (2H)-carboxylate

HRID 627104Notes

Reaction equation

HRID 627104 reaction equation
[Si:1]([O:8][CH2:9][C@@H:10]1[CH:15]=[CH:14][C:13](=[O:16])[CH2:12][N:11]1[C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].O.C(=O)([O-])[O-].[K+].[K+].[I:31]I>CN(C)C1C=CN=CC=1.C1COCC1.CCOCC>[Si:1]([O:8][CH2:9][C@@H:10]1[CH:15]=[C:14]([I:31])[C:13](=[O:16])[CH2:12][N:11]1[C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2]

Participants

8

Reactant 4

HCID 807IodineHCID 962WaterHCID 11430Potassium CarbonateHCID 89852524(S)-Tert-butyl 2-(((tert-butyldimethylsilyl)oxy)methyl)-5-oxo-5,6-dihydropyridine-1(2H)-carboxylate2×

Product 1

HCID 131735281(S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-4-iodo-5-oxo-5,6-dihydropyridine-1 (2H)-carboxylateYield 85%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a solution of (S)-tert-butyl 2-((tert-butyldimethylsilyloxy)methyl)-5-oxo-5,6-dihydropyridine-1(2H)-carboxylate (Intermediate 50, 10 g, 29.28 mmol) and 4-dimethylaminopyridine (0.894 g, 7.32 mmol) in THF (100 mL)/water (100 mL) at room temperature was added potassium carbonate (3.24 g, 23.42 mmol) and iodine (8.92 g, 35.14 mmol). After stirring for 15 minutes, the reaction mixture was diluted with ether and washed with saturated sodium thiosulfate twice, then 5% citric acid and brine. The organics were dried over magnesium sulfate, filtered and concentrated. Silica gel chromatography (0%-15% ethyl acetate/hexanes) afforded the desired product as a tan oil (11.6 g, 85%).

Workup

  1. washwashed with saturated sodium thiosulfate twice
  2. dry with materialThe organics were dried over magnesium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-e473d07d7e37416993c5abe339c5265d
Source dataset
uspto-grants-2016_04
Patent number
US09309245B2

Reaction notes

Loading…