Binap, (A+-)- → HCID 66760282, compound

HRID 1850390Notes

Reaction equation

HRID 1850390 reaction equation
[N:1]1([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:7][CH2:6][CH2:5][NH:4][CH2:3][CH2:2]1.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.CC(C)([O-])C.[Na+].Br[C:68]1[C:69]([CH3:82])=[C:70]([CH3:81])[C:71]2[O:75][C:74]([CH3:77])([CH3:76])[C:73](=[O:78])[C:72]=2[C:79]=1[CH3:80]>O.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C=CC=CC=1>[CH3:76][C:74]1([CH3:77])[C:73](=[O:78])[C:72]2[C:79]([CH3:80])=[C:68]([N:4]3[CH2:5][CH2:6][CH2:7][N:1]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:2][CH2:3]3)[C:69]([CH3:82])=[C:70]([CH3:81])[C:71]=2[O:75]1

Participants

8

Reactant 4

HCID 634876Binap, (A+-)-HCID 2756058Tert-butyl 1,4-diazepane-1-carboxylateHCID 22935579HCID 22935579, compoundHCID 23676156Sodium t-butoxide

Product 1

HCID 66760282HCID 66760282, compoundYield 14%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

tert-butyl 1,4-diazepane-1-carboxylate (2.50 g, 12.5 mmol), palladium acetate (70.0 mg, 0.312 mmol), BINAP (579 mg, 0.901 mmol) and sodium tert-butoxide (1.79 g, 18.6 mmol) were added to a solution of toluene (20 mL) containing 5-bromo-2,2,4,6,7-pentamethyl-1-benzofuran-3(2H)-one (1.77 g, 6.25 mmol) synthesized in Reference Example 36, and the mixture was heated to reflux under argon atmosphere for 29 hours. After cooled to room temperature, the mixture was diluted with water and extracted using ethyl acetate. It was dried using anhydrous magnesium sulfate. After that, the solvent was removed under reduced pressure, and the obtained residue was purified by silica gel column chromatography (hexane-ethyl acetate: 100:0 to 95:5) to give 340 mg of the title compound (yield: 14%).

Workup

  1. customsynthesized in Reference Example 36
  2. temperaturethe mixture was heated
  3. temperatureto reflux under argon atmosphere for 29 hours
  4. extractionextracted
  5. customIt was dried
  6. customAfter that, the solvent was removed under reduced pressure
  7. customthe obtained residue was purified by silica gel column chromatography (hexane-ethyl acetate: 100:0 to 95:5)

Sources & evidence

ORD record
ord-a2d8b53977e340d38f607886c55223b2
Source dataset
uspto-grants-2015_02
Patent number
US08957069B2

Reaction notes

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