Cesium carbonate → HCID 58292555, compound

HRID 1798194Notes

Reaction equation

HRID 1798194 reaction equation
[CH2:1]([O:3][C:4](=[O:18])[CH2:5][CH:6]1[O:10][B:9]([OH:11])[C:8]2[CH:12]=[C:13]([OH:17])[CH:14]=[C:15]([CH3:16])[C:7]1=2)[CH3:2].C(=O)([O-])[O-].[Cs+].[Cs+].[Cl:25][C:26]1[N:31]=[C:30](Cl)[CH:29]=[CH:28][N:27]=1>CN(C=O)C>[CH2:1]([O:3][C:4](=[O:18])[CH2:5][CH:6]1[O:10][B:9]([OH:11])[C:8]2[CH:12]=[C:13]([O:17][C:28]3[CH:29]=[CH:30][N:31]=[C:26]([Cl:25])[N:27]=3)[CH:14]=[C:15]([CH3:16])[C:7]1=2)[CH3:2]

Participants

5

Reactant 3

HCID 10796Cesium carbonateHCID 775312,4-DichloropyrimidineHCID 58292549Ethyl 2-(1,6-dihydroxy-4-methyl-1,3-dihydrobenzo[c][1,2]oxaborol-3-yl)acetate

Product 1

HCID 58292555HCID 58292555, compoundYield 63%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

A solution of (1,6-dihydroxy-4-methyl-1,3-dihydro-benzo[c][1,2]oxaborol-3-yl)-acetic acid ethyl ester (3.30 g, 13.20 mmol) in DMF (10 mL) was treated with cesium carbonate (13.30 g, 40.82 mmol) at 0° C. followed by 2,4-dichloropyrimidine (3.90 g, 26.20 mmol). The mixture was stirred at room temperature for 24 hours. The suspension was quenched with ice water, acidified with 2N HCl and extracted with ethyl acetate. The extracts were dried (Na2SO4), filtered and concentrated in vacuo. The residue was purified by silica gel flash column chromatography (EtOAc/hexane; 1:1 then MeOH/CH2Cl2; 1:99 gradient) to give [6-(2-chloro-pyrimidin-4-yloxy)-1-hydroxy-4-methyl-1,3-dihydro-benzo[c][1,2]oxaborol-3-yl]-acetic acid ethyl ester as a yellow foam (3.00 g, 63%). 1H NMR (400 MHz, CD3OD) δ 8.48 (d, J=5.85 Hz, 1H), 7.22 (s, 1H), 7.10 (s, 1H), 6.98 (d, J=5.85 Hz, 1H), 5.65 (dd, J=8.20, 2.73 Hz, 1H), 4.14-4.07 (m, 2H), 3.18 (dd, J=15.22, 2.73 Hz, 1H), 2.52 (dd, J=15.22, 8.20 Hz, 1H), 2.39 (s, 3H), 1.19 (t, J=7.03 Hz, 3H).

Workup

  1. customThe suspension was quenched with ice water
  2. extractionextracted with ethyl acetate
  3. dry with materialThe extracts were dried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified by silica gel flash column chromatography (EtOAc/hexane

Sources & evidence

ORD record
ord-63f6c9ef0f3040e99022ff341d38ec37
Source dataset
uspto-grants-2013_01
Patent number
US08343944B2

Reaction notes

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