Lithium Hexamethyldisilazide → HCID 68800867, compound

HRID 2099583Notes

Reaction equation

HRID 2099583 reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([CH2:7][C:8]2[CH:9]=[N:10][CH:11]=[CH:12][CH:13]=2)[CH:2]=1.C[Si]([N-][Si](C)(C)C)(C)C.[Li+].[C:24]1([C:30]([C:38]2[CH:43]=[CH:42][CH:41]=[CH:40][CH:39]=2)=[N:31][S:32]([C:34]([CH3:37])([CH3:36])[CH3:35])=[O:33])[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1>C1COCC1>[C:24]1([C:30]([NH:31][S@:32]([C:34]([CH3:37])([CH3:36])[CH3:35])=[O:33])([C:38]2[CH:39]=[CH:40][CH:41]=[CH:42][CH:43]=2)[CH:7]([C:8]2[CH:9]=[N:10][CH:11]=[CH:12][CH:13]=2)[C:3]2[CH:2]=[N:1][CH:6]=[CH:5][CH:4]=2)[CH:25]=[CH:26][CH:27]=[CH:28][CH:29]=1

Participants

5

Reactant 3

HCID 2733832Lithium HexamethyldisilazideHCID 147626403,3'-MethylenedipyridineHCID 86028185HCID 86028185, compound

Product 1

HCID 68800867HCID 68800867, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

In a flame dried flask under N2, 3-(pyridin-3-ylmethyl)pyridine (0.072 g, 0.42 mmol) was dissolved in THF (3 mL). The solution was cooled to 0° C. Lithium bis(trimethylsilyl)-amide (1 M solution in THF, 0.465 mL, 0.47 mmol) was slowly added and the reaction was stirred at 0° C. for 15 min. The reaction became dark red. A solution of N-(diphenylmethylene)-2-methylpropane-2-sulfinamide (0.121 g, 0.42 mmol) in THF (1 mL) was slowly added drop-wise. The reaction was stirred at 0° C. for 1 hr then removed from the ice bath. Sat. aq. NH4Cl (20 mL) was added and the reaction was stirred vigorously. The product was extracted with EtOAc (3×50 mL). The combined organics were dried over Na2SO4, filtered and concentrated to afford an oil which was purified by flash column chromatography (0-5% MeOH/CH2Cl2). The fractions were combined and concentrated in vacuo to afford the title compound as a white solid. (S) Enantiomer at Sulfur: 1H NMR (CD3OD) δ 8.49 (d, 1H, J=2.20 Hz), 8.46 (dd, 1H, J=1.46 Hz), 8.36 (dd, 1H, J=5.37 Hz), 8.30 (d, 1H, J=2.20 Hz), 7.49-7.33 (m, 11H), 7.25-7.23 (m, 3H), 5.78 (s, 1H), 1.08 (s, 1H ). HRMS m/z (M+H) found: 478.1920 (M+Na).

Workup

  1. customIn a flame dried flask under N2
  2. stirringThe reaction was stirred at 0° C. for 1 hr
  3. customthen removed from the ice bath
  4. additionSat. aq. NH4Cl (20 mL) was added
  5. stirringthe reaction was stirred vigorously
  6. extractionThe product was extracted with EtOAc (3×50 mL)
  7. dry with materialThe combined organics were dried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customto afford an oil which
  11. customwas purified by flash column chromatography (0-5% MeOH/CH2Cl2)
  12. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-919c196a810243baa7aa932b7cb57fd2
Source dataset
uspto-grants-2009_08
Patent number
US07569589B2

Reaction notes

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