3-Buten-2-one,4-(4-CF3-phenyl)- → HCID 46915337, compound

HRID 2109759Notes

Reaction equation

HRID 2109759 reaction equation
[F:1][C:2]([F:15])([F:14])[C:3]1[CH:8]=[CH:7][C:6](/[CH:9]=[CH:10]/[C:11](=[O:13])[CH3:12])=[CH:5][CH:4]=1.B1(C)OC(C2C=CC=CC=2)(C2C=CC=CC=2)[C@@H]2N1CCC2.[B]1OC2C(=CC=CC=2)O1>C1(C)C=CC=CC=1>[F:1][C:2]([F:14])([F:15])[C:3]1[CH:4]=[CH:5][C:6](/[CH:9]=[CH:10]/[C@@H:11]([OH:13])[CH3:12])=[CH:7][CH:8]=1

Participants

5

Reactant 3

HCID 57088533-Buten-2-one,4-(4-CF3-phenyl)-HCID 6327445Benzcatechinborane2×HCID 9838490(R)-2-Methyl-CBS-oxazaborolidine

Product 1

HCID 46915337HCID 46915337, compoundYield 99.1%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent3×

Conditions

Temperature
-78 °C

Procedure

(E)-4-(4-(trifluoromethyl)phenyl)but-3-en-2-one (15 g, 70 mmol) was taken up in 500 mL of toluene. (R)-2-Methyl-CBS-oxazaborolidine, 1.09 M in toluene (6.4 mL, 7.0 mmol) was added, and the mixture was chilled to −78° C. Catecholborane (13 mL, 119 mmol) was added dropwise via addition funnel in 125 mL of toluene. The mixture was stirred for 25 minutes and then gradually warmed to −45° C. and stirred for 2 hours. The yellow color taken on during the catecholborane addition faded during this time and the solution cleared. The mixture was quenched with 300 mL of water and warmed to room temperature. The mixture was partitioned in a separatory funnel. The organic portion was washed 3 times with 200 mL of 5% aq. KOH (to remove the catechol), twice with 200 mL of 10% aq. HCl (to remove the (R)-2-methyl-CBS-oxazaborolidine catalyst), and once with 200 mL of brine, then dried over MgSO4. Filtration and concentration under reduced pressure afforded (S,E)-4-(4-(trifluoromethyl)phenyl)but-3-en-2-ol (15 g, 99% yield) as a yellow oil that slowly crystallized on the bench top. 1H NMR (400 MHz, CDCl3) δ ppm 7.57 (d, J=8.22 Hz, 2H) 7.50-7.45 (m, 2H) 6.62 (d, J=16.04 Hz, 1H) 6.36 (dd, J=16.04, 6.06 Hz, 1H) 4.49-4.57 (m, 1H) 1.61 (d, J=4.30 Hz, 1H) 1.39 (d, J=6.46 Hz, 3H).

Workup

  1. temperaturegradually warmed to −45° C.
  2. stirringstirred for 2 hours
  3. customThe mixture was quenched with 300 mL of water
  4. temperaturewarmed to room temperature
  5. customThe mixture was partitioned in a separatory funnel
  6. washThe organic portion was washed 3 times with 200 mL of 5% aq. KOH (
  7. customto remove the catechol), twice with 200 mL of 10% aq. HCl (
  8. customto remove the (R)-2-methyl-CBS-oxazaborolidine catalyst), and once with 200 mL of brine
  9. dry with materialdried over MgSO4
  10. filtrationFiltration and concentration under reduced pressure

Sources & evidence

ORD record
ord-296e42654606413d8c9d0f035ef06f8a
Source dataset
uspto-grants-2009_04
Patent number
US07514566B2

Reaction notes

Loading…