Triethylamine → HCID 54173502, compound

HRID 52271Notes

Reaction equation

HRID 52271 reaction equation
[CH:1]1([N:5]([C@@H:10]2[CH2:15][C:14]3[C:16](OS(C(F)(F)F)(=O)=O)=[CH:17][CH:18]=[C:19]([F:20])[C:13]=3[O:12][CH2:11]2)[CH:6]2[CH2:9][CH2:8][CH2:7]2)[CH2:4][CH2:3][CH2:2]1.[C]=O.C(N(CC)CC)C.CN([CH:41]=[O:42])C.[CH3:43][OH:44]>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH:6]1([N:5]([C@@H:10]2[CH2:15][C:14]3=[C:16]([C:43]([O:42][CH3:41])=[O:44])[CH:17]=[CH:18][C:19]([F:20])=[C:13]3[O:12][CH2:11]2)[CH:1]2[CH2:4][CH2:3][CH2:2]2)[CH2:9][CH2:8][CH2:7]1

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 21901440N,N-dimethylformamide methanolHCID 54291217HCID 54291217, compoundHCID 178418416HCID 178418416, compound

Product 1

HCID 54173502HCID 54173502, compoundYield 78%

Reagents, catalysts & solvents 2

HCID 812191,3-Bis(diphenylphosphino)propaneCatalystHCID 167845palladium(II) acetateCatalyst

Conditions

Temperature
70 °C

Procedure

(R)-3-(N,N-Dicyclobutylamino)-8-fluoro-5-trifluoromethylsulfonyloxy-3,4-dihydro-2H-1-benzopyran (0.82 g, 1.94 mmol) was dissolved in a solution of DMF/methanol (6:2, 15 mL) and then degassed followed by the inlet of carbonmonoxide (×3). With a slight positive pressure of carbonmonoxide, palladium(II)-acetate (14 mg), 1,3-bis(diphenylphosphino)propane (25 mg) and triethylamine (0.60 mL, 4.3 mmol) were added and the reaction mixture was degassed and subjected to carbonmonoxide once again. The reaction was heated to 70° C. under carbornmonoxide atmosphere with vigorous stirring for 5.5 h. The reaction was allowed to cool and the solvent was removed in vacuo. The remains were taken into a 2M solution of NH3 and then extracted, twice, with diethyl ether. The combined ether portions were dried (MgSO4), filtered, and the solvent removed in vacuo to give the crude residue. Chromatography on silica (eluent: 12.5% ethyl acetate/hexane) gave 501 mg (78% yield) of the title compound as a clear oil. [α]21D =-138.2° (C=0.1; CHCl3) GC-MS (70 eV) M=333 (4%).

Workup

  1. customdegassed
  2. customthe reaction mixture was degassed
  3. temperatureto cool
  4. customthe solvent was removed in vacuo
  5. extractionextracted
  6. dry with materialThe combined ether portions were dried (MgSO4)
  7. filtrationfiltered
  8. customthe solvent removed in vacuo
  9. customto give the crude residue

Sources & evidence

ORD record
ord-72181d53373b48c1a20ae7edae0aae3d
Source dataset
uspto-grants-1997_04
Patent number
US05616610

Reaction notes

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