p-Toluenesulfonic acid → HCID 20817533, compound

HRID 131616Notes

Reaction equation

HRID 131616 reaction equation
[Cl:1][C:2]([Cl:37])([Cl:36])[CH2:3][O:4][C:5](=[O:35])[O:6][CH:7]([CH:24]([CH3:34])[CH2:25][O:26][CH2:27][C:28]1[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=1)[CH:8]([CH3:23])[C:9](=[O:22])[C:10]([CH3:21])([CH3:20])[CH:11](OC(C)C)[O:12]C(C)C.CC1C=CC(S(O)(=O)=O)=CC=1.C([O-])(O)=O.[Na+]>C1COCC1.O>[Cl:1][C:2]([Cl:36])([Cl:37])[CH2:3][O:4][C:5](=[O:35])[O:6][CH:7]([CH:24]([CH3:34])[CH2:25][O:26][CH2:27][C:28]1[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=1)[CH:8]([CH3:23])[C:9](=[O:22])[C:10]([CH3:21])([CH3:20])[CH:11]=[O:12]

Participants

5

Reactant 3

HCID 6101p-Toluenesulfonic acidHCID 516892Sodium BicarbonateHCID 66850227HCID 66850227, compound

Product 1

HCID 20817533HCID 20817533, compoundYield 76%

Reagents, catalysts & solvents 1

HCID 21881883Oxolane--water (1/1)Solvent

Conditions

Temperature
70 °C

Procedure

To solution of 32a (1.28 g, 2.25 mmol) in 4:1 THF/H2O (25 mL) was added p-TsOH (111.0 mg, 0.6 mmol). After heating at 70° C. 5 h, the reaction mixture was poured into a cold (0° C.) sat. NaHCO3 aq solution (12 mL) and then extracted with EtOAc. The combined organic layers were washed with brine, dried over MgSO4 and concentrated under reduced pressure. The crude product was purified by flash chromatography (gradient hexane to hexane/EtOAc 84:16) to give 67 (793.2 mg, 76%) as a clear oil: 1H NMR (400 MHz, CDCl3) □ 0.90 (d, J=5.8 Hz, 3H), 1.0 (d, J=6.9 Hz, 3H), 1.24 (s, 6H), 1.97-2.04 (m, 1H), 3.24 (dd, J=4.8 and 9.2 Hz, 1H), 3.34 (m, 1H), 3.42 (dd, J=5.8 and 9.2 Hz, 1H), 4.35 (d, J=11.9 Hz, 1H), 4.39 (d, J=11.9 Hz, 1H), 4.64 (d, J=11.9 Hz, 1H), 4.69 (d, J=11.9 Hz, 1H), 4.96 (t, J=6.0 Hz, 1H), 7.19-7.28 (m, 5H), 9.49 (s, 1H); 13C NMR (100 MHz, CDCl3) −12.0, 14.8, 19.5, 19.6, 35.4, 43.3, 60.9, 71.1, 73.3, 80.37, 94.5, 127.7, 127.8, 128.3, 137.9, 154.1, 201.0, 210.1; IR (film, NaCl, cm−1) 2973, 2880, 1758, 1701, 1453, 1380, 1248; LRMS (ESI) calcd for C21H27O6Cl3Na [M+Na+] 503.0, found 503.0; [α]23D=−18.5 (c=0.8, CHCl3).

Workup

  1. extractionextracted with EtOAc
  2. washThe combined organic layers were washed with brine
  3. dry with materialdried over MgSO4
  4. concentrationconcentrated under reduced pressure
  5. customThe crude product was purified by flash chromatography (gradient hexane to hexane/EtOAc 84:16)

Sources & evidence

ORD record
ord-6e374318c6e7495a8a26cb8dfdcbb315
Source dataset
uspto-grants-2008_06
Patent number
US07384964B2

Reaction notes

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