Potassium Phosphate, Tribasic → HCID 67080529, compound

HRID 1021410Notes

Reaction equation

HRID 1021410 reaction equation
[C:1]([O:5][C:6]([C:8]1[CH:30]=[CH:29][C:11]([O:12][C:13]2[CH:22]=[C:21]3[C:16]([CH:17]([C:23]([O:25][CH2:26][CH3:27])=[O:24])[CH2:18][CH2:19][O:20]3)=[CH:15][C:14]=2Cl)=[C:10]([N+:31]([O-:33])=[O:32])[CH:9]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].P([O-])([O-])([O-])=O.[K+].[K+].[K+].C1(P([CH:55]2[CH2:60][CH2:59]CCC2)C2CCCCC2)CCCCC1.C1(B(O)O)CC1>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[C:1]([O:5][C:6]([C:8]1[CH:30]=[CH:29][C:11]([O:12][C:13]2[CH:22]=[C:21]3[C:16]([CH:17]([C:23]([O:25][CH2:26][CH3:27])=[O:24])[CH2:18][CH2:19][O:20]3)=[CH:15][C:14]=2[CH:59]2[CH2:60][CH2:55]2)=[C:10]([N+:31]([O-:33])=[O:32])[CH:9]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

8

Reactant 4

HCID 62657Potassium Phosphate, TribasicHCID 75806TricyclohexylphosphineHCID 2760897Cyclopropylboronic acidHCID 67080355HCID 67080355, compound

Product 1

HCID 67080529HCID 67080529, compoundYield 69.5%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

To a stirred solution of ethyl 7-(4-(tert-butoxycarbonyl)-2-nitrophenoxy)-6-chlorochroman-4-carboxylate (1.38 g, 2.89 mmol) in toluene (15 mL) was added successively water (0.75 mL), potassium phosphate (3.06 g, 14.4 mmol), tricyclohexylphosphine (0.32 g, 1.16 mmol), and cyclopropylboronic acid (0.74 g, 8.7 mm3ol). The resulting mixture was stirred and a balloon of nitrogen with a three-way purge valve was attached, and the flask was evacuated and refilled five times with nitrogen. Palladium(II) acetate (0.13 g, 0.58 mmol) was added, and again the flask was evacuated and refilled five times with nitrogen. The mixture was stirred in an oil bath set to 110° C. under the nitrogen balloon for 16 hours. The mixture was cooled to ambient temperature, and diluted with ethyl acetate (100 mL) and water (50 mL). The organic layer was dried over sodium sulfate and concentrated. The residue was purified by chromatography on silica gel, eluting with 95/5 hexanes/ethyl acetate, to afford ethyl 7-(4-(tert-butoxycarbonyl)-2-nitrophenoxy)-6-cyclopropylchroman-4-carboxylate as a yellow oil (0.39 g, 28%).

Workup

  1. customa balloon of nitrogen with a three-way purge valve
  2. customthe flask was evacuated
  3. additionrefilled five times with nitrogen
  4. customagain the flask was evacuated
  5. additionrefilled five times with nitrogen
  6. stirringThe mixture was stirred in an oil bath
  7. additiondiluted with ethyl acetate (100 mL) and water (50 mL)
  8. dry with materialThe organic layer was dried over sodium sulfate
  9. concentrationconcentrated
  10. customThe residue was purified by chromatography on silica gel
  11. washeluting with 95/5 hexanes/ethyl acetate

Sources & evidence

ORD record
ord-fce78c0c17bd4265bed3d2465b7eed54
Source dataset
uspto-grants-2014_05
Patent number
US08716498B2

Reaction notes

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