Water → tert-butyl (7-phenyl-2-oxo-2,3,4,5-tetrahydro-1H-1-benzazepin-3-yl)carbamate

HRID 1670410Notes

Reaction equation

HRID 1670410 reaction equation
[C:1]1(B(O)O)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C(=O)([O-])[O-].[Cs+].[Cs+].O.Br[C:18]1[CH:19]=[CH:20][C:21]2[NH:27][C:26](=[O:28])[CH:25]([NH:29][C:30](=[O:36])[O:31][C:32]([CH3:35])([CH3:34])[CH3:33])[CH2:24][CH2:23][C:22]=2[CH:37]=1>[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].O1CCOCC1>[C:1]1([C:18]2[CH:19]=[CH:20][C:21]3[NH:27][C:26](=[O:28])[CH:25]([NH:29][C:30](=[O:36])[O:31][C:32]([CH3:33])([CH3:35])[CH3:34])[CH2:24][CH2:23][C:22]=3[CH:37]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

7

Reactant 4

HCID 962WaterHCID 10796Cesium carbonateHCID 66827Phenylboronic AcidHCID 57655892tert-butyl (7-bromo-2-oxo-2,3,4,5-tetrahydro-1H-benzo[b]azepin-3-yl)carbamate

Product 1

HCID 57655891tert-butyl (7-phenyl-2-oxo-2,3,4,5-tetrahydro-1H-1-benzazepin-3-yl)carbamate

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

371 mg of phenylboronic acid (3.04 mmol), 62 mg of 1,1′-bis(diphenylphosphino)ferrocene palladium chloride (C35H30Cl4FeP2Pd, Mw 816.65, 0.025 mmol) and 3.96 g of caesium carbonate (12.16 mmol) are introduced into a 100 ml round-bottomed flask, with stirring and under an argon atmosphere, containing 22 ml of water, 6.5 ml of dioxane and 1.08 g of 10 (3.04 mmol). The medium is heated at 100° C., with stirring, for 1 h. The medium is filtered over celite and washed with 10 ml of dioxane, 10 ml of CH2Cl2 and 10 ml of MeOH. The filtrate is concentrated under vacuum. 25 ml of EtOAc are then added and the mixture is washed with 2 times 25 ml of water. The organic phase is dried over MgSO4, filtered and evaporated to dryness. The crude is chromatographed on a silica cartridge (50 g), elution being carried out with CH2Cl2/MeOH (as an MeOH gradient: 1 to 10%). 350 mg of expected product 13 (white solid) are recovered.

Workup

  1. stirringwith stirring, for 1 h
  2. filtrationThe medium is filtered over celite
  3. washwashed with 10 ml of dioxane, 10 ml of CH2Cl2 and 10 ml of MeOH
  4. concentrationThe filtrate is concentrated under vacuum
  5. addition25 ml of EtOAc are then added
  6. washthe mixture is washed with 2 times 25 ml of water
  7. dry with materialThe organic phase is dried over MgSO4
  8. filtrationfiltered
  9. customevaporated to dryness
  10. customThe crude is chromatographed on a silica cartridge (50 g), elution
  11. custom350 mg of expected product 13 (white solid) are recovered

Sources & evidence

ORD record
ord-879d019ed03e4612a4b863800ed4b6ef
Source dataset
uspto-grants-2011_08
Patent number
US07994162B2

Reaction notes

Loading…