HCID 131725388, compound → HCID 69640538, compound

HRID 1744219Notes

Reaction equation

HRID 1744219 reaction equation
[CH3:1][O:2][C:3]1[CH:20]=[CH:19][C:18]2[C@@H:17]3[C@H:8]([C@H:9]4[C@@:13]([CH2:15][CH2:16]3)([CH3:14])[C@@H:12]([O:21][CH2:22][O:23][CH3:24])[CH2:11][CH:10]4[CH2:25]OS(CC3C=CC=CC=3)(=O)=O)[CH2:7][CH2:6][C:5]=2[CH:4]=1>C1COCC1>[CH3:1][O:2][C:3]1[CH:20]=[CH:19][C:18]2[C@@H:17]3[C@H:8]([C@H:9]4[C@@:13]([CH2:15][CH2:16]3)([CH3:14])[C@@H:12]([O:21][CH2:22][O:23][CH3:24])[CH2:11][C@@H:10]4[CH3:25])[CH2:7][CH2:6][C:5]=2[CH:4]=1

Participants

3

Reactant 1

HCID 131725388HCID 131725388, compound

Product 1

HCID 69640538HCID 69640538, compoundYield 97.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
65 °C

Procedure

A solution of 15.8 mg (0.0269 mmol) of 58 in anhydrous THF (500 μL) was stirred at rt as 108 μL of a 1 M solution of LiEt3BH in THF (0.108 mmol) was added and the reaction was stirred and heated at 65° C. for 5 h then quenched at rt with EtOH (1 mL). To the reaction mixture was added diglyme (2 mL), 48 mg (0.431 mmol) Et3NO and the reaction was stirred and heated at 150° C. for 1 h allowing the THF to evaporate. The reaction mixture was allowed to cool to rt, poured into H2O (50 mL) and extracted with EtOAc (3×, 50 mL). Combined organic extracts were washed with 10% Na2S2O5 (30 mL), H2O (30 mL), dried over Na2SO4 and concentrated in vacuo giving a colorless oil. Purification by flash chromatography on a 2×17 cm column of silica gel using 4:1 hexanes/EtOAc as eluent gave 9 mg (97%) of 59. Data for 59: TLC, T-1, Rf 0.73; 1H NMR (400 MHz, CDCl3) δ 0.86 (s, 3H, H-18), 0.90 (t, 1H, J=10.2 Hz, H-14), 1.12 (d, 3H, J=6.2 Hz, 15α-CH3), 3.38 (s, 3H, CH2OCH3), 3.64 (t, 1H, J=8.6 Hz, H-17α), 3.79 (s, 3H, ArOCH3), 4.65–4.67 (AB quartet, 2H, JAB=6.6 Hz, OCH2O), 6.62 (d, 1H, J=2.8 Hz, H-4), 6.72 (dd, 1H, J=8.6, 2.8 Hz, H-2), 7.22 (d, 1H, J=8.6 Hz, H-1).

Workup

  1. additionwas added
  2. customthen quenched at rt with EtOH (1 mL)
  3. additionTo the reaction mixture was added diglyme (2 mL), 48 mg (0.431 mmol) Et3NO
  4. stirringthe reaction was stirred
  5. temperatureheated at 150° C. for 1 h
  6. customto evaporate
  7. temperatureto cool to rt
  8. additionpoured into H2O (50 mL)
  9. extractionextracted with EtOAc (3×, 50 mL)
  10. washCombined organic extracts were washed with 10% Na2S2O5 (30 mL), H2O (30 mL)
  11. dry with materialdried over Na2SO4
  12. concentrationconcentrated in vacuo
  13. customgiving a colorless oil
  14. customPurification by flash chromatography on a 2×17 cm column of silica gel using 4:1 hexanes/EtOAc as eluent

Sources & evidence

ORD record
ord-5d72f2328a8c4703a9d98ef1352ac23a
Source dataset
uspto-grants-2006_03
Patent number
US07015211B2

Reaction notes

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