Benzophenone imine → HCID 131730368, compound

HRID 1483066Notes

Reaction equation

HRID 1483066 reaction equation
[C:1]([SiH2:5][O:6][C:7]([CH3:16])([CH3:15])[C:8]1[CH:9]=[CH:10][C:11](Cl)=[N:12][CH:13]=1)([CH3:4])([CH3:3])[CH3:2].C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.[C:63](=[NH:76])([C:70]1[CH:75]=[CH:74][CH:73]=[CH:72][CH:71]=1)[C:64]1[CH:69]=[CH:68][CH:67]=[CH:66][CH:65]=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C:63](=[N:76][C:11]1[CH:10]=[CH:9][C:8]([C:7]([CH3:16])([CH3:15])[O:6][SiH2:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[CH:13][N:12]=1)([C:70]1[CH:71]=[CH:72][CH:73]=[CH:74][CH:75]=1)[C:64]1[CH:69]=[CH:68][CH:67]=[CH:66][CH:65]=1

Participants

7

Reactant 4

HCID 136809Benzophenone imineHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 178455429HCID 178455429, compound

Product 1

HCID 131730368HCID 131730368, compound

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Conditions

Temperature
80 °C

Procedure

5-(tert-butyl dimethyl silanyloxymethyl)-2-chloro pyridine (5.58 g, 21.6 mmol), BINAP (0.4 g, 0.64 mmol) and benzophenone imine (4.7 g, 25.9 mmol) are dissolved in toluene (50 ml) and the solution is degassed with nitrogen. Sodium t-butoxide (2.91 g, 30.3 mmol) and Pd2(dba)3 (0.2 g, 0.22 mmol) are added and the solution is degassed once more. The mixture is heated at 80° C. for 6 h and then allowed to cool to rt. The mixture is diluted 4-fold with Et2O and then the solution is filtered. Evaporation of solvent in vacuo gave the crude benzhydrylidene-[5-(tert-butyl dimethyl silanyloxymethyl)-pyridin-2-yl]-amine. This product is dissolved in MeOH (50 ml) and hydroxylamine (2.85 ml of a 50% aq. Solution, 46.5 mmol) and the solution stirred at rt for 16 h. The mixture is concentrated in vacuo and then the residue is dissolved in Et2O (50 ml) and filtered. The filtrate is ished with brine, dried (MgSO4) and then the solvent is evaporated in vacuo. The crude red oil is purified by SiO2 chromatography (gradient Petrol Ether:EtOAc=8:1 to 100% EtOAc) to give an orange oil which crystallized when triturated with hexane. The solvent is finally removed in vacuo to give 5-(tert-butyl dimethyl silanyloxymethyl)-pyridin-2-ylamine as an orange solid (2.9 g, 56.1%). MS (ESI) m/z 239.2 (M+H)+

Workup

  1. customthe solution is degassed with nitrogen
  2. customthe solution is degassed once more
  3. temperatureto cool to rt
  4. additionThe mixture is diluted 4-fold with Et2O
  5. filtrationthe solution is filtered
  6. customEvaporation of solvent in vacuo

Sources & evidence

ORD record
ord-41b502f54f9e4c29bcf9e9a3bc14e3e7
Source dataset
uspto-grants-2016_08
Patent number
US09416136B2

Reaction notes

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