Cesium fluoride → HCID 135674225, compound

HRID 1008252Notes

Reaction equation

HRID 1008252 reaction equation
Br[C:2]1[CH:10]=[C:9]2[C:5](/[C:6](=[CH:12]/[C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][N:14]=3)/[C:7](=[O:11])[NH:8]2)=[CH:4][CH:3]=1.[CH3:19][O:20][C:21]1[CH:26]=[C:25](B2OC(C)(C)C(C)(C)O2)[CH:24]=[CH:23][C:22]=1[OH:36].[F-].[Cs+]>COCCOC.CO.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[OH:36][C:22]1[CH:23]=[CH:24][C:25]([C:2]2[CH:10]=[C:9]3[C:5](/[C:6](=[CH:12]/[C:13]4[CH:18]=[CH:17][CH:16]=[CH:15][N:14]=4)/[C:7](=[O:11])[NH:8]3)=[CH:4][CH:3]=2)=[CH:26][C:21]=1[O:20][CH3:19]

Participants

6

Reactant 3

HCID 25953Cesium fluorideHCID 27346502-Methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenolHCID 69920733HCID 69920733, compound

Product 1

HCID 135674225HCID 135674225, compoundYield 19%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 86595564Dimethoxyethane methanolSolvent

Procedure

A solution of Example 2A (80 mg, 0.26 mmol), 2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (78 mg, 0.31 mmol), Pd(PPh3)4 (30 mg, 0.026 mmol), and CsF (43 mg, 0.29 mmol) in DME/methanol (2:1) was stirred at 80° C. for 18 hours, cooled to room temperature, concentrated, and extracted with ethyl acetate. The combined extracts were washed with brine, dried (MgSO4), filtered, and concentrated. The concentrate was purified by HPLC (Zorbax C-18 column) with 10-100% acetonitrile/water to provide the desired product (17 mg, 18%). MS (DCI/NH3) m/z 345.1 (M+H)+; 1H NMR (300 MHz, CD3OD) δ8.92 (d, 1H, J=5.5 Hz), 8.82 (d, 1H, J=7.8 Hz), 8.25 (s, 1H), 7.89 (m, 1H), 7.71 (s, 1H), 7.62 (m, 1H), 7.41 (m, 1H), 7.24 (d, 1H, J=1.7 Hz), 7.14 (dd, 1H, J=8.1, 2.0 Hz), 7.08 (dd, 1H, J=5.8, 2.1 Hz), 6.99 (d, 1H, J=8.1 Hz), 3.98 (s, 3H); Anal. Calcd. for C21H16N2O3.1.5CF3CO2H: C, 73.24; H, 4.68; N, 8.13. Found: C, 56.40; H, 3.57; N, 5.005.

Workup

  1. concentrationconcentrated
  2. extractionextracted with ethyl acetate
  3. washThe combined extracts were washed with brine
  4. dry with materialdried (MgSO4)
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe concentrate was purified by HPLC (Zorbax C-18 column) with 10-100% acetonitrile/water

Sources & evidence

ORD record
ord-f1bdff521d194cac9df5240ccc19ea92
Source dataset
uspto-grants-2004_09
Patent number
US06797825B2

Reaction notes

Loading…