tert-Butylsulfinamide, (R)-(+)- → HCID 86689869, compound

HRID 2409063Notes

Reaction equation

HRID 2409063 reaction equation
[C:1]([C:4]1[N:9]=[C:8]2[C:10]([Cl:20])=[CH:11][N:12]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[C:7]2=[CH:6][CH:5]=1)(=O)[CH3:2].[CH3:21][C:22]([S@:25]([NH2:27])=[O:26])([CH3:24])[CH3:23]>C1COCC1.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[C:22]([S@:25]([N:27]=[C:1]([C:4]1[N:9]=[C:8]2[C:10]([Cl:20])=[CH:11][N:12]([C:13]([O:15][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:14])[C:7]2=[CH:6][CH:5]=1)[CH3:2])=[O:26])([CH3:24])([CH3:23])[CH3:21].[C:22]([S@:25]([N:27]=[C:1]([C:4]1[N:9]=[C:8]2[C:10]([Cl:20])=[CH:11][N:12]([C:13]([O:15][CH2:16][CH3:19])=[O:14])[C:7]2=[CH:6][CH:5]=1)[CH3:2])=[O:26])([CH3:24])([CH3:23])[CH3:21]

Participants

6

Reactant 2

HCID 10964479tert-Butylsulfinamide, (R)-(+)-HCID 86689867HCID 86689867, compound

Product 2

HCID 86689868HCID 86689868, compoundYield 29.88%HCID 86689869HCID 86689869, compoundYield 56.59%

Reagents, catalysts & solvents 2

HCID 76524Titanium tetraethoxideCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
75 °C

Procedure

To tert-butyl 5-acetyl-3-chloro-1H-pyrrolo[3,2-b]pyridine-1-carboxylate (2.90 g, 9.84 mmol) and (R)-2-methylpropane-2-sulfinamide (1.79 g, 14.76 mmol) dissolved in anhydrous THF (96 mL) was added titanium (IV) ethoxide (5.16 mL, 24.60 mmol) at RT under N2. The reaction mixture was then stirred at 75° C. under N2 for 16 h. Volatile solvent was removed under reduced pressure, and the crude residue was diluted with EtOAc (−250 mL). The reaction mixture was vigorously stirred while a saturated solution of brine (−40 mL) was slowly added. The reaction mixture was stirred for 15 min and filtered through a pad of Celite®. The organic layer from the filtrate was washed with water and brine, dried (Na2SO4), filtered, and concentrated under reduced pressure. The crude product was purified by SiO2 chromatography eluting with EtOAc/heptane to afford 1.17 g (29.88%) of (R)-tert-butyl 5-(1-((tert-butylsulfinyl)imino)ethyl)-3-chloro-1H-pyrrolo[3,2-b]pyridine-1-carboxylate and 2.06 g (56.59%) of (R)-ethyl 5-(1-((tert-butylsulfinyl)imino)ethyl)-3-chloro-1H-pyrrolo[3,2-b]pyridine-1-carboxylate.

Workup

  1. customVolatile solvent was removed under reduced pressure
  2. additionthe crude residue was diluted with EtOAc (−250 mL)
  3. stirringThe reaction mixture was vigorously stirred while a saturated solution of brine (−40 mL)
  4. additionwas slowly added
  5. stirringThe reaction mixture was stirred for 15 min
  6. filtrationfiltered through a pad of Celite®
  7. washThe organic layer from the filtrate was washed with water and brine
  8. dry with materialdried (Na2SO4)
  9. filtrationfiltered
  10. concentrationconcentrated under reduced pressure
  11. customThe crude product was purified by SiO2 chromatography
  12. washeluting with EtOAc/heptane

Sources & evidence

ORD record
ord-3ced8fd283bc45488bc7bb5583c7d6a5
Source dataset
uspto-grants-2014_08
Patent number
US08815877B2

Reaction notes

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