1,3-Bis(diphenylphosphino)propane → HCID 66799181, compound

HRID 1193263Notes

Reaction equation

HRID 1193263 reaction equation
Br[C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][CH2:7][C@H:8]2[NH:11][C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[C:4]([F:19])[CH:3]=1.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>CO.CC([O-])=O.CC([O-])=O.[Pd+2]>[C:14]([O:13][C:12]([NH:11][C@H:8]1[C:9]2[C:5](=[C:4]([F:19])[CH:3]=[C:2]([C:12]([O:13][CH3:14])=[O:18])[CH:10]=2)[CH2:6][CH2:7]1)=[O:18])([CH3:17])([CH3:16])[CH3:15]

Participants

5

Reactant 2

HCID 812191,3-Bis(diphenylphosphino)propaneHCID 66805459HCID 66805459, compound

Product 1

HCID 66799181HCID 66799181, compoundYield 83%

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 887MethanolSolvent

Procedure

(R)-tert-Butyl 6-bromo-4-fluoro-2,3-dihydro-1H-inden-1-ylcarbamate (1.1 g, 3.33 mol, 1.0 eq.) was dissolved in MeOH (35 ml) and DMSO (30 ml), and the mixture was degassed for 30 minutes with argon. Pd(OAc)2 (0.038 g, 0.166 mmol, 0.05 eq.), 1,3-bis(diphenylphosphino)-propane (0.068 g, 0.166 mmol, 0.05 eq.) and TEA (1.39 ml, 9.99 mmol, 3.0 eq.) were then added, and stirring was carried out for 16 hours in a pressure vessel at 75° C. under CO pressure (80 psi). The reaction mixture was concentrated, diluted with water (50 ml) and extracted with ethyl acetate (2×75 ml). The combined org. phases were washed with sat. NaCl solution (60 ml), dried over sodium sulfate, concentrated under reduced pressure and purified by column chromatography (silica gel, 10% ethyl acetate in hexane). Yield: 83% (0.86 g, 2.783 mmol)

Workup

  1. customDMSO (30 ml), and the mixture was degassed for 30 minutes with argon
  2. concentrationThe reaction mixture was concentrated
  3. additiondiluted with water (50 ml)
  4. extractionextracted with ethyl acetate (2×75 ml)
  5. washphases were washed with sat. NaCl solution (60 ml)
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated under reduced pressure
  8. custompurified by column chromatography (silica gel, 10% ethyl acetate in hexane)

Sources & evidence

ORD record
ord-79d3d3bd6c914e04a6281f85ead49272
Source dataset
uspto-grants-2014_03
Patent number
US08680159B2

Reaction notes

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