4-Bromobiphenyl → Biphenyl

HRID 1369615Notes

Reaction equation

HRID 1369615 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)=[CH:4][CH:3]=1.C(N(CC)CC)C>CN(C=O)C.C(OCC)(=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(C)C=CC=CC=1P(C1C=CC=CC=1C)C1C=CC=CC=1C>[C:5]1([C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][CH:13]=2)[CH:6]=[CH:7][CH:2]=[CH:3][CH:4]=1

Participants

7

Reactant 2

HCID 71014-BromobiphenylHCID 8471Triethylamine

Product 1

HCID 7095BiphenylYield 170.2%

Reagents, catalysts & solvents 4

HCID 80271Tri-o-tolylphosphineCatalystHCID 167845palladium(II) acetateCatalystHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
100 °C

Procedure

To a solution of 4.75 g (12.7 mmol) of N-(2R-(t-Butoxycarbonyl)methyl-4-pentenoyl)-4S-phenylmethyl-2-oxazolidinone, 3.73 g (16.0 mmol) of 4-bromobiphenyl, 0.234 g (0.77 mmol) of tri-o-tolylphosphine, and 2.22 mL (1.62 g, 16.0 mmol) of triethylamine in 10 mL of anhydrous DMF under argon was added 0.086 g (0.385 mmol) of palladium(II) acetate. The solution was heated at 100° C. for 4 h, cooled to room temperature, diluted with ethyl acetate. The precipitate was removed by filtration, and the filtrate was partitioned between 150 mL of 2:1 ethyl acetate:hexane and 50 mL of pH 7 phosphate buffer (0.5 M) containing a little sodium sulfite. The organic layer was washed with 0.2 N aq. sodium bisulfate and brine/pH 7 phosphate buffer, dried over sodium sulfate, and concentrated. The residue was dissolved in 50 mL of ethyl acetate, diluted with 250 mL of isooctane, and seeded with a few crystals of the product. The solid was removed by filtration, and recrystallized from 250 mL of 4:1 isooctane:ethyl acetate to give 4.20 g (63%) of the product, N-(2R-(t-Butoxycarbonyl)methyl-(5-(biphen-4-yl)-4-pentenoyl)-4S-phenylmethyl-2-oxazolidinone, as fine white needles: mp 118-119° C.; 1H NMR (300 MHz, CDCl3) 7.25-7.60 (m, 14H), 6.47 (d, 1H, J=16 Hz), 6.25 (dt, 1H, J=16 and 8 Hz), 4.65-4.70 (m, 1H), 4.34-4.44 (m, 1H), 4.11 (dd, 1H, J=9 and 2 Hz), 4.01 (t, 1H, J=8 Hz), 3.33 (dd, 1H, J=14 and 3 Hz), 2.89 (dd, 1H, J=17 and 11 Hz), 2.76 (dd, 1H, J=14 and 10 Hz), 2.40-2.57 (m, 3H), 1.43 (s, 9H).

Workup

  1. temperaturecooled to room temperature
  2. customThe precipitate was removed by filtration
  3. customthe filtrate was partitioned between 150 mL of 2:1 ethyl acetate
  4. additionhexane and 50 mL of pH 7 phosphate buffer (0.5 M) containing a little sodium sulfite
  5. washThe organic layer was washed with 0.2 N aq. sodium bisulfate and brine/pH 7 phosphate buffer
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated
  8. dissolutionThe residue was dissolved in 50 mL of ethyl acetate
  9. additiondiluted with 250 mL of isooctane
  10. customThe solid was removed by filtration
  11. customrecrystallized from 250 mL of 4:1 isooctane

Sources & evidence

ORD record
ord-57c38a3cb0704515a09b70815c1f05d4
Source dataset
uspto-grants-2003_06
Patent number
US06579890B1

Reaction notes

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