Triethylamine → HCID 18790118, compound

HRID 1107136Notes

Reaction equation

HRID 1107136 reaction equation
[CH2:1]([CH:8]1[CH2:12][O:11][C:10](=[O:13])[N:9]1[C:14](=[O:25])[CH2:15][CH2:16][CH2:17][S:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[O-]S(C(F)(F)F)(=O)=O.C([B+]CCCC)CCC.C(N(CC)CC)C.[C:50]1([CH2:56][CH2:57][CH2:58][CH2:59][CH:60]=[O:61])[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=1>C(Cl)Cl>[CH2:1]([CH:8]1[CH2:12][O:11][C:10](=[O:13])[N:9]1[C:14](=[O:25])[CH:15]([CH2:16][CH2:17][S:18][C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)[CH:60]([OH:61])[CH2:59][CH2:58][CH2:57][CH2:56][C:50]1[CH:55]=[CH:54][CH:53]=[CH:52][CH:51]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 4

HCID 8471TriethylamineHCID 561886BenzenepentanalHCID 18790149HCID 18790149, compoundHCID 178418657HCID 178418657, compound

Product 1

HCID 18790118HCID 18790118, compoundYield 68.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-78 °C

Procedure

To a solution containing (+)-4-benzyl-3-(4-phenylsulfanylbutanoyl)oxazolidin-2-one (2 g, 5.63 mmol) in anhydrous CH2Cl2 (30 mL) under nitrogen atmosphere at 0° C. is added di-n-butyl boron triflate (1 M in CH2Cl2, 6.6 mL, 6.59 mmol). To the resulting brown solution is added triethylamine (1 mL, 7.38 mmol). The pale yellow solution is cooled to -78° C. and a solution of 5-phenyl-1-pentanal (1 g, 6.25 mmol) in CH2Cl2 (5 mL) is added via syringe. The mixture is stirred at -78° C. for 1 hour and at 0° C. for 45 minutes then is quenched by the dropwise addition of 3:1 methanol/pH 7 phosphate buffer (40 mL) followed by 2:1 methanol/30% H2O2 (30 mL). The biphasic mixture is stirred at 0° C. for 1 hour then is combined with an identical reaction performed on 1.3 g-scale and evaporated to 50% volume in vacuo. The residue is partitioned between 5% NaHCO3 (200 mL) and diethyl ether (200 mL) and the layers are separated. The aqueous phase is extracted with diethyl ether (200 mL). The combined organic extracts are washed successively with 5% NaHCO3 (3×100 mL), 5% Na2S2O3 (3×100 mL), water (100 mL), brine (100 mL), dried over anhydrous MgSO4, filtered and concentrated to afford a yellow oil which is chromatographed on silica gel (pet-ether/EtOAc 9:1→4:1) to provide (+)-4-benzyl-3-[3-hydroxy-7-phenyl-2-(2-phenylsulfanylethyl)heptanoyl]-oxazolidin-2-one (2 g, 43%) as a colorless oil. TLC analysis [pet-ether/EtOAc, 4:1, Rf (oxazolidinone)=0.50, Rf (aldol product)=0.20]. [α]23D +7.2° (c 1.3, CHCl3). 1H NMR (300 MHz, CDCl3) δ 1.50-1.60 (m, 7H), 1.90 (m, 1H), 2.20 (m, 1H), 2.31 (d, J=3.6 Hz, 1H), 2.58 (t, J=7.5 Hz), 2.67 (dd, J=13.3, 9.9 Hz), 2.85 (m, 1H), 3.00 (m, 1H), 3.32 (dd, J=13.3, 3.4 Hz), 3.88 (m, 1H), 4.20 (m, 2H), 4.65 (m, 1H), 7.1-7.35 (m, 15H) ppm. Mass spectrum (FAB) m/z 517 (M)+.

Workup

  1. customthen is quenched by the dropwise addition of 3:1 methanol/pH 7 phosphate buffer (40 mL)
  2. stirringThe biphasic mixture is stirred at 0° C. for 1 hour
  3. customthen is combined with an identical reaction
  4. customevaporated to 50% volume in vacuo
  5. customThe residue is partitioned between 5% NaHCO3 (200 mL) and diethyl ether (200 mL)
  6. customthe layers are separated
  7. extractionThe aqueous phase is extracted with diethyl ether (200 mL)
  8. washThe combined organic extracts are washed successively with 5% NaHCO3 (3×100 mL), 5% Na2S2O3 (3×100 mL), water (100 mL), brine (100 mL)
  9. dry with materialdried over anhydrous MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customto afford a yellow oil which
  13. customis chromatographed on silica gel (pet-ether/EtOAc 9:1→4:1)

Sources & evidence

ORD record
ord-d330dfe5e0454f878dc0eadef3917f77
Source dataset
uspto-grants-2000_05
Patent number
US06057369

Reaction notes

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