Lithium tri-s-butylborohydride → HCID 86689870, compound

HRID 2409064Notes

Reaction equation

HRID 2409064 reaction equation
[C:1]([S@:5]([N:7]=[C:8]([C:10]1[N:15]=[C:14]2[C:16]([Cl:24])=[CH:17][N:18](C(OCC)=O)[C:13]2=[CH:12][CH:11]=1)[CH3:9])=[O:6])([CH3:4])([CH3:3])[CH3:2].CCC(C)[BH-](C(C)CC)C(C)CC.[Li+]>C1COCC1>[Cl:24][C:16]1[C:14]2=[N:15][C:10]([C@@H:8]([NH:7][S@@:5]([C:1]([CH3:2])([CH3:4])[CH3:3])=[O:6])[CH3:9])=[CH:11][CH:12]=[C:13]2[NH:18][CH:17]=1

Participants

4

Reactant 2

HCID 3611392Lithium tri-s-butylborohydrideHCID 86689869HCID 86689869, compound

Product 1

HCID 86689870HCID 86689870, compoundYield 65.03%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To (R)-ethyl 5-(1-((tert-butylsulfinyl)imino)ethyl)-3-chloro-1H-pyrrolo[3,2-b]pyridine-1-carboxylate (2.06 g, 5.569 mmol) in anhydrous THF (36.2 mL) at 0° C. was added dropwise L-selectride (1.0 mol/L) in THF (8.4 mL). The resultant orange reaction mixture was then warmed to RT and stirred at this temperature under N2 for 16 h. Volatile solvent was removed under reduced pressure, and the crude residue was diluted with EtOAc. The EtOAc layer was washed with sat'd. aq. NaHCO3, water and brine, dried (Na2SO4), filtered, and concentrated under reduced pressure. The crude product was purified by SiO2 chromatography eluting with MeOH/EtOAc+1% TEA. Trituration with DCM afforded 1.08 g (65.03%) of (R)—N—((S)-1-(3-chloro-1H-pyrrolo[3,2-b]pyridin-5-yl)ethyl)-2-methylpropane-2-sulfinamide as pale yellow solid (100% ee). 1H NMR (400 MHz, DMSO) δ 11.52 (s, 1H), 7.80 (d, J=8.5 Hz, 1H), 7.77 (s, 1H), 7.29 (d, J=8.5 Hz, 1H), 5.43 (d, J=5.4 Hz, 1H), 4.62-4.51 (m, 1H), 1.53 (d, J=6.8 Hz, 3H), 1.11 (s, 9H); MS (ESI) m/z: 300.0 [M+1]+.

Workup

  1. customVolatile solvent was removed under reduced pressure
  2. additionthe crude residue was diluted with EtOAc
  3. washThe EtOAc layer was washed with sat'd
  4. dry with materialaq. NaHCO3, water and brine, dried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe crude product was purified by SiO2 chromatography
  8. washeluting with MeOH/EtOAc+1% TEA

Sources & evidence

ORD record
ord-e18ee30da80f427aa99ece471ffd6891
Source dataset
uspto-grants-2014_08
Patent number
US08815877B2

Reaction notes

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