Diisopropylamine → HCID 66962784, compound

HRID 1360125Notes

Reaction equation

HRID 1360125 reaction equation
C(NC(C)C)(C)C.[Li]CCCC.[N:13]1[CH:18]=[CH:17][CH:16]=[C:15]([CH2:19][C:20]2[CH:21]=[N:22][CH:23]=[CH:24][CH:25]=2)[CH:14]=1.[C:26]([C:28]1[CH:29]=[C:30]([CH:34]=[N:35][S@:36]([C:38]([CH3:41])([CH3:40])[CH3:39])=[O:37])[CH:31]=[CH:32][CH:33]=1)#[N:27]>C1COCC1>[C:26]([C:28]1[CH:29]=[C:30]([CH:34]([NH:35][S:36]([C:38]([CH3:41])([CH3:40])[CH3:39])=[O:37])[CH:19]([C:20]2[CH:21]=[N:22][CH:23]=[CH:24][CH:25]=2)[C:15]2[CH:14]=[N:13][CH:18]=[CH:17][CH:16]=2)[CH:31]=[CH:32][CH:33]=1)#[N:27]

Participants

6

Reactant 4

HCID 7912DiisopropylamineHCID 147626403,3'-MethylenedipyridineHCID 66962498HCID 66962498, compoundHCID 178418339Butyllithium

Product 1

HCID 66962784HCID 66962784, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

In a flame dried flask under N2, diisopropylamine (1.647 mL, 11.75 mmol) was dissolved in anhydrous THF (5 mL) and the solution was cooled to 0° C. nBuLi (2.5 M solution in hexanes, 4.406 mL, 11.02 mmol) was added and the reaction was stirred at 0° C. for 15 min. A solution of 3-(pyridin-3-ylmethyl)pyridine (1.250 g, 7.34 mmol) in anhydrous THF (15 mL) was slowly added and the reaction became dark red. After 15 min, a solution of (S)—N-[(3-cyanophenyl)methylidene]-2-methylpropane-2-sulfinamide (1.893 g, 8.08 mmol) in anhydrous THF (10 mL) was added. The reaction was stirred at 0° C. for 2.5 h and was quenched with saturated aqueous NH4Cl (150 mL). The product was extracted with ethyl acetate (4×100 mL). The combined organics were dried over Na2SO4, filtered, concentrated in vacuo and purified by reverse phase HPLC (DeltaPak C18, 47 mm×300 mm, 15 □, 0% CH3OH/100% H2O to 100% CH3OH/0% H2O). The fractions containing each diastereomer were separately combined and concentrated in vacuo to afford N-[1-(3-cyanophenyl)-2,2-dipyridin-3-ylethyl]-2-methylpropane-2-sulfinamide as two diastereomers;

Workup

  1. customIn a flame dried flask under N2
  2. additionwas added
  3. waitAfter 15 min
  4. stirringThe reaction was stirred at 0° C. for 2.5 h
  5. customwas quenched with saturated aqueous NH4Cl (150 mL)
  6. extractionThe product was extracted with ethyl acetate (4×100 mL)
  7. dry with materialThe combined organics were dried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. custompurified by reverse phase HPLC (DeltaPak C18, 47 mm×300 mm, 15 □, 0% CH3OH/100% H2O to 100% CH3OH/0% H2O)
  11. additionThe fractions containing each diastereomer
  12. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-daf1c811a2f24796a781e6af8b11a4b6
Source dataset
uspto-grants-2011_02
Patent number
US07879839B2

Reaction notes

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