2-Dicyclohexylphosphino-2',4',6'-triisoprophylbiphenyl → Tert-butyl [4-(benzyloxy)-2-chlorophenyl]acetate

HRID 1474673Notes

Reaction equation

[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12](Br)=[C:11]([Cl:16])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Cl-].[C:18]([O:22][C:23](=[O:26])[CH2:24][Zn+])([CH3:21])([CH3:20])[CH3:19].CC(C1C=C(C(C)C)C(C2C=CC=CC=2P(C2CCCCC2)C2CCCCC2)=C(C(C)C)C=1)C>C1COCC1.C(OCC)(=O)C.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]>[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][C:12]([CH2:24][C:23]([O:22][C:18]([CH3:21])([CH3:20])[CH3:19])=[O:26])=[C:11]([Cl:16])[CH:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

Conditions

Temperature: 60 °C

Procedure

To a solution of 4-(benzyloxy)-1-bromo-2-chlorobenzene (1 g, 3.36 mmol) in THF (10 ml) was added 2-tert-butoxy-2-oxoethylzinc chloride (13.44 ml, 6.72 mmol). Nitrogen gas bubbled through the mixture for 10 min. Pd2(dba)3 (0.154 g, 0.180 mmol) and X-PHOS (0.160 g, 0.336 mmol) were added and the resulting mixture heated at 60° C. for 50 min. The mixture was cooled, diluted with ethyl acetate (20 mL), washed with aqueous ammonium chloride (saturated, 1×15 mL), dried over MgSO4, filtered and the solvent evaporated under reduced pressure. The residue was purified by column chromatography on silica gel Biotage 50M, using a gradient eluant of EtOAc/Hexane (0-20%) to afford the title compound. LC/MS (m/z): 333 (M+H)+.

Workup

customNitrogen gas bubbled through the mixture for 10 min
temperatureThe mixture was cooled
washwashed with aqueous ammonium chloride (saturated, 1×15 mL)
dry with materialdried over MgSO4
filtrationfiltered
customthe solvent evaporated under reduced pressure
customThe residue was purified by column chromatography on silica gel Biotage 50M

Sources & evidence

ORD record: ord-7cc225b74bd04fe28410c1388a2d980f
Source dataset: uspto-grants-2015_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09018224B2

Reaction notes

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