Triisopropyl phosphite → HCID 67076954, compound

HRID 899433Notes

Reaction equation

HRID 899433 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:6]=[C:7]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH:8]=[C:9]2[C:14]=1[O:13][C:12](=[O:15])[CH:11]=[CH:10]2)=[O:4].C(O[CH2:28][C:29](=[CH2:35])[CH2:30][Si](C)(C)C)(=O)C.P(OC(C)C)(OC(C)C)OC(C)C>C1COCC1.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:1][O:2][C:3]([C:5]1[CH:6]=[C:7]([O:16][CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH:8]=[C:9]2[C:14]=1[O:13][C:12](=[O:15])[CH:11]1[CH2:30][C:29](=[CH2:28])[CH2:35][CH:10]21)=[O:4]

Participants

6

Reactant 3

HCID 8304Triisopropyl phosphiteHCID 44283472-(Trimethylsilylmethyl)allyl acetateHCID 59685168HCID 59685168, compound

Product 1

HCID 67076954HCID 67076954, compound

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of preparation 4 (198 mg, 0.64 mmol) and Pd(OAc)2 (17 mg, 0.076 mmol) in 4 mL THF add 2-(acetoxymethyl)allyl-trimethylsilane (0.163 mL, 0.122 mmol) followed by triisopropyl phosphite (0.12 mL, 0.49 mmol). After stirring at 60° C. overnight, cool the solution to room temperature, concentrate under reduced pressure, and dilute with EtOAc. Wash the solution with saturated aqueous sodium bicarbonate and brine. Dry over Na2SO4, and then concentrate to an oil. Purify the material by silica gel chromatography (10 g, 10 to 30% EtOAc/Hex over 30 min at 35 mL/min) to give 80 mg (0.208 mol, 63%) of preparation 6 and 30 mg (0.091 mmol, 27%) of recovered starting material. 1H NMR (400 MHz, CDCl3) δ 7.48-7.36 (m, 6H), 7.01 (d, 1H, J=3.1 Hz), 5.10 (s, 2H), 5.01 (m, 2H), 3.97 (s, 3H), 3.43 (dt, 1H, J=7.5, 3.1 Hz), 3.21-3.10 (m, 2H), 2.86-2.74 (m, 2H), 2.43 (m, 1H).

Workup

  1. temperaturecool the solution to room temperature
  2. concentrationconcentrate under reduced pressure
  3. additiondilute with EtOAc
  4. washWash the solution with saturated aqueous sodium bicarbonate and brine
  5. dry with materialDry over Na2SO4
  6. concentrationconcentrate to an oil
  7. customPurify the material by silica gel chromatography (10 g, 10 to 30% EtOAc/Hex over 30 min at 35 mL/min)
  8. customto give
  9. custom80 mg (0.208 mol, 63%) of preparation 6 and 30 mg (0.091 mmol, 27%)
  10. customof recovered

Sources & evidence

ORD record
ord-af9dbffe209e483e85d2a3b4c7caaf86
Source dataset
uspto-grants-2008_04
Patent number
US07354951B2

Reaction notes

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