Triethylamine → (4R)-3-[(2R,3S,4S,5S,6S,7Z)-3-hydroxy-5-[(4-methoxyphenyl)methoxy]-2,4,6-trimethyl-1-oxo-7,9-decadienyl]-4-(phenylmethyl)-2-oxazolidinone

HRID 857965Notes

Reaction equation

HRID 857965 reaction equation
[CH2:1]([C@@H:8]1[CH2:12][O:11][C:10](=[O:13])[N:9]1[C:14](=[O:17])[CH2:15][CH3:16])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.B(OS(C(F)(F)F)(=O)=O)(CCCC)CCCC.CCN(CC)CC.[CH3:42][O:43][C:44]1[CH:49]=[CH:48][C:47]([CH2:50][O:51][C@@H:52]([C@@H:57]([CH3:62])/[CH:58]=[CH:59]\[CH:60]=[CH2:61])[C@@H:53]([CH3:56])[CH:54]=[O:55])=[CH:46][CH:45]=1>C(Cl)Cl>[OH:55][C@@H:54]([C@H:53]([CH3:56])[C@@H:52]([O:51][CH2:50][C:47]1[CH:46]=[CH:45][C:44]([O:43][CH3:42])=[CH:49][CH:48]=1)[C@@H:57]([CH3:62])/[CH:58]=[CH:59]\[CH:60]=[CH2:61])[C@@H:15]([CH3:16])[C:14]([N:9]1[C@H:8]([CH2:1][C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[CH2:12][O:11][C:10]1=[O:13])=[O:17]

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 2724243Methanesulfonic acid, 1,1,1-trifluoro-, anhydride with B,B-dibutylborinic acidHCID 10966403(R)-(-)-4-Benzyl-3-propionyl-2-oxazolidinoneHCID 11044422(2R,3S,4S,5Z)-3-[(4-methoxyphenyl)methoxy]-2,4-dimethyl-5,7-octadienal

Product 1

HCID 86760329(4R)-3-[(2R,3S,4S,5S,6S,7Z)-3-hydroxy-5-[(4-methoxyphenyl)methoxy]-2,4,6-trimethyl-1-oxo-7,9-decadienyl]-4-(phenylmethyl)-2-oxazolidinoneYield 96.4%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of (R)-4-benzyl-3-propionyl-2-oxazolidinone (2.18 g, 9.34 mmol) and methylene chloride (15 mL) is cooled to −20° C. (n-Bu)2BOTf (1.0 M in DCM, 8.7 mL, 8.7 mmol) is introduced dropwise. The reaction is allowed to warm to 0° C. NEt3 (1.15 9, 11.34 mmol) is added and the mixture is stirred at 0° C. for 1 h, then cooled to −78° C. A solution of (2R,3S,4S,5Z)-3-[(4-methoxyphenyl)methoxy]-2,4-dimethyl-5,7-octadienal (1.95 g, 6.77 mmol) in DCM (10 mL) is added dropwise at −70° C. for 10 min. After 1 h at −74° C., the mixture is warmed to 0° C. The reaction is quenched with pH 7 buffer (15 mL). The mixture is slowly treated with a solution of 30% H2O2 in MeOH (1:2, 15 mL) at 0° C., stirred for 40 min at room temperature, and concentrated. The residue is extracted with ethyl acetate (3×100 mL). The combined organic phase is washed with saturated aqueous NaHCO3, brine, and concentrated. Flash chromatography gives the desired compound (3.4 g, 96.4%) as a clear oil.

Workup

  1. additionis introduced dropwise
  2. temperaturecooled to −78° C
  3. waitAfter 1 h at −74° C.
  4. temperaturethe mixture is warmed to 0° C
  5. customThe reaction is quenched with pH 7 buffer (15 mL)
  6. additionThe mixture is slowly treated with a solution of 30% H2O2 in MeOH (1:2, 15 mL) at 0° C.
  7. stirringstirred for 40 min at room temperature
  8. concentrationconcentrated
  9. extractionThe residue is extracted with ethyl acetate (3×100 mL)
  10. washThe combined organic phase is washed with saturated aqueous NaHCO3, brine
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-32cd1ba5dbd045d49bcd131590dc2fdb
Source dataset
uspto-grants-2006_12
Patent number
US07148218B2

Reaction notes

Loading…