tert-Butylsulfinamide, (R)-(+)- → HCID 86689830, compound

HRID 2409018Notes

Reaction equation

HRID 2409018 reaction equation
[C:1]([C:4]1[N:9]=[C:8]2[CH:10]=[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].[CH3:20][C:21]([S@:24]([NH2:26])=[O:25])([CH3:23])[CH3:22]>C1COCC1.[O-]CC.[Ti+4].[O-]CC.[O-]CC.[O-]CC>[C:21]([S@:24]([N:26]=[C:1]([C:4]1[N:9]=[C:8]2[CH:10]=[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:25])([CH3:23])([CH3:22])[CH3:20]

Participants

5

Reactant 2

HCID 10964479tert-Butylsulfinamide, (R)-(+)-HCID 86689829HCID 86689829, compound

Product 1

HCID 86689830HCID 86689830, compoundYield 53.7%

Reagents, catalysts & solvents 2

HCID 76524Titanium tetraethoxideCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
75 °C

Procedure

To a solution of tert-butyl 5-acetylpyrrolo[3,2-b]pyridine-1-carboxylate (2.0 g, 7.68 mmol) and (R)-2-methylpropane-2-sulfinamide (1.04 g, 8.45 mmol) dissolved in anhydrous THF (50 mL) was added titanium (IV) ethoxide (3.2 mL, 15.37 mmol) at RT under a N2 atmosphere. The reaction mixture was stirred at 75° C. under N2 for 16 h. The solvent was removed in vacuo and the crude residue was diluted with EtOAc (ca. 100 mL). The reaction mixture was vigorously stirred while a saturated solution of brine (−20 mL) was added slowly. 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 in vacuo. The crude product was purified by SiO2 chromatography eluting with EtOAc/heptane to afford 1.50 g (53.7%) of (R)-tert-butyl 5-(1-(tert-butylsulfinylimino)-ethyl)-1H-pyrrolo[3,2-b]pyridine-1-carboxylate as yellow solid: 1H NMR (400 MHz, CDCl3) δ 8.38 (d, J=8.6 Hz, 1H), 8.16 (d, J=8.8 Hz, 1H), 7.88 (d, J=3.8 Hz, 1H), 6.83 (d, J=3.8 Hz, 1H), 2.94 (s, 3H), 1.69 (s, 9H), 1.35 (s, 9H); MS (ESI) m/z: 364.3 [M+1]+.

Workup

  1. customThe solvent was removed in vacuo
  2. additionthe crude residue was diluted with EtOAc (ca. 100 mL)
  3. stirringThe reaction mixture was vigorously stirred while a saturated solution of brine (−20 mL)
  4. additionwas added slowly
  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 in vacuo
  11. customThe crude product was purified by SiO2 chromatography
  12. washeluting with EtOAc/heptane

Sources & evidence

ORD record
ord-05eecd1d488946e58023c0eb06dcb487
Source dataset
uspto-grants-2014_08
Patent number
US08815877B2

Reaction notes

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