Triisopropyl phosphite → HCID 68877610, compound

HRID 732310Notes

Reaction equation

HRID 732310 reaction equation
[CH3:1][O:2][CH2:3][O:4][C:5]1[CH:6]=[C:7]2[C:12](=[CH:13][CH:14]=1)[O:11][C:10](=[O:15])[CH:9]=[CH:8]2.C(O[CH2:20][C:21](=[CH2:27])[CH2:22][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][CH2:3][O:4][C:5]1[CH:14]=[CH:13][C:12]2[O:11][C:10](=[O:15])[CH:9]3[CH2:22][C:21](=[CH2:20])[CH2:27][CH:8]3[C:7]=2[CH:6]=1

Participants

6

Reactant 3

HCID 8304Triisopropyl phosphiteHCID 44283472-(Trimethylsilylmethyl)allyl acetateHCID 12083970HCID 12083970, compound

Product 1

HCID 68877610HCID 68877610, compound

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
60 °C

Procedure

To a solution of 6-methoxymethoxy coumarin 17a (21 g, 0.102 mol) and Pd(OAc)2 (2.75 g, 0.012 mol) in 500 mL THF add 2-(acetoxymethyl)allyl-trimethylsilane (26 mL, 0.122 mol) followed by triisopropyl phosphite (18.1 mL, 0.073 mol). After stirring at 60° C. overnight, cool the solution to RT, 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 (Biotage 40M+65M columns, 10 to 30% EtOAc/Hex over 60 min at 50 mL/min followed by 30 to 50% EtOAc/Hex over 60 min at 50 mL/min) to give 18.3 g (0.070 mol, 69%) of cyclopentanoid 18 and 3.8 g (18.3 mmol, 18%) of recovered starting material. HRMS (ES+) calc for C15H17O4: 261.1127, found: 261.1122 (M+1).

Workup

  1. temperaturecool the solution to RT
  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 (Biotage 40M+65M columns, 10 to 30% EtOAc/Hex over 60 min at 50 mL/min followed by 30 to 50% EtOAc/Hex over 60 min at 50 mL/min)
  8. customto give 18.3 g (0.070 mol, 69%) of cyclopentanoid 18 and 3.8 g (18.3 mmol, 18%)
  9. customof recovered

Sources & evidence

ORD record
ord-e2cc757c89db414395900be21db183cd
Source dataset
uspto-grants-2009_09
Patent number
US07585985B2

Reaction notes

Loading…