Potassium Phosphate, Tribasic → HCID 86687551, compound

HRID 1473496Notes

Reaction equation

HRID 1473496 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[C:7]([C:9]([F:12])([F:11])[F:10])[CH:6]=[CH:5][C:4]=1B(O)O.[Br:16][C:17]1[CH:18]=[CH:19][C:20]([CH:27]=[O:28])=[C:21]([CH:26]=1)[C:22]([O:24]C)=O.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>C1CC=CCCC=C1.C1CC=CCCC=C1.[Cl-].[Cl-].[Rh].[Rh].C1COCC1>[Br:16][C:17]1[CH:26]=[C:21]2[C:20]([CH:27]([C:4]3[CH:5]=[CH:6][C:7]([C:9]([F:12])([F:11])[F:10])=[CH:8][C:3]=3[O:2][CH3:1])[O:28][C:22]2=[O:24])=[CH:19][CH:18]=1

Participants

6

Reactant 3

HCID 62657Potassium Phosphate, TribasicHCID 24901776(2-Methoxy-4-(trifluoromethyl)phenyl)boronic acidHCID 53419722Methyl 5-bromo-2-formylbenzoate

Product 1

HCID 86687551HCID 86687551, compoundYield 86%

Reagents, catalysts & solvents 2

HCID 6436379Rhodium, di-mu-chlorobis((1,2,5,6-eta)-1,5-cyclooctadiene)di-CatalystHCID 8028TetrahydrofuranSolvent

Procedure

2-Methoxy-4-(trifluoromethyl)phenyl boronic acid (2.05 g, 9.32 mmol; Combi-Blocks, San Diego, Calif.), methyl 5-bromo-2-formylbenzoate (1.51 g, 6.21 mmol; GLSyntech, LLC, Hatfield, Pa.), tripotassium phosphate (5.27 g, 24.9 mmol; freshly ground) and THF (31.1 mL) was added to a vial. The vial was purged with argon. Then chloro(1,5-cyclooctadiene)rhodium(i) dimer (0.153 g, 0.311 mmol; Strem Chemicals, Inc., Newburyport, Mass.) was added. The vial was sealed and stirred at RT. After 1 h, the reaction was filtered and the filtrate was concentrated under a vacuum. The crude material was absorbed onto a plug of silica gel and purified by chromatography through a silica gel column (80 g), eluting with a gradient of 0% to 10% EtOAc in heptane, to provide 6-bromo-3-(2-methoxy-4-(trifluoromethyl)phenyl)isobenzofuran-1(3H)-one (2.06 g, 86% yield) as a brown solid. 1H NMR (400 MHz, CDCl3) δ ppm 3.92 (s, 3H), 6.72 (s, 1H), 7.11-7.17 (m, 3H), 7.25 (dt, J=8.2, 0.7 Hz, 1H), 7.65 (dd, J=8.3, 1.7 Hz, 1H), 8.00 (d, J=1.8 Hz, 1H). m/z (ESI) 405.0 (M+H)+. This lactone was not stable on MS.

Workup

  1. customThe vial was purged with argon
  2. customThe vial was sealed
  3. filtrationthe reaction was filtered
  4. concentrationthe filtrate was concentrated under a vacuum
  5. customThe crude material was absorbed onto a plug of silica gel
  6. custompurified by chromatography through a silica gel column (80 g)
  7. washeluting with a gradient of 0% to 10% EtOAc in heptane

Sources & evidence

ORD record
ord-9e09b2551997426f87863583891f7362
Source dataset
uspto-grants-2015_04
Patent number
US09012443B2

Reaction notes

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