Hydrochloric Acid → HCID 58292542, compound

HRID 1798029Notes

Reaction equation

HRID 1798029 reaction equation
C[Si](Cl)(C)C.Br[CH2:7][C:8]([O:10][CH2:11][CH3:12])=[O:9].[CH2:13]([C:15]1[CH:22]=[C:21]([O:23]C2CCCCO2)[CH:20]=[C:19]([B:30]2[O:34][C:33](C)(C)C(C)(C)[O:31]2)[C:16]=1C=O)[CH3:14].Cl>C1COCC1.[Zn]>[CH2:11]([O:10][C:8](=[O:9])[CH2:7][CH:33]1[O:34][B:30]([OH:31])[C:19]2[CH:20]=[C:21]([OH:23])[CH:22]=[C:15]([CH2:13][CH3:14])[C:16]1=2)[CH3:12]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 6397ChlorotrimethylsilaneHCID 7748Ethyl bromoacetateHCID 86653969HCID 86653969, compound

Product 1

HCID 58292542HCID 58292542, compoundYield 27%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
55 °C

Procedure

To a suspension of zinc dust (5.35 g, 82.3 mmol) in THF (10 mL) was added trimethylsilyl chloride (1.1 g, 10.15 mmol) at 40° C. The mixture was heated to 55° C. and stirred for 45 minutes. After cooling down to 37° C., ethyl bromoacetate (7.58 mL, 74.87 mmol) was slowly added to the reaction mixture at 37-40° C. After addition, the resulting mixture was allowed to cool to room temperature over 30 minutes. This solution was added to a solution of 2-ethyl-4-(tetrahydro-pyran-2-yloxy)-6-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzaldehyde (2.07 g, 5.39 mmol) in THF (6 mL) at 0° C. The mixture was stirred for 10 minutes before treating with 3 N HCl and extracted with EtOAc (2×25 mL). The organic extracts were washed with brine, dried over anhydrous MgSO4 and concentrated in vacuo. The residue was purified by silica gel flash column chromatography and lyophilized to give (4-ethyl-1,6-dihydroxy-1,3-dihydro-benzo[c][1,2]oxaborol-3-yl)-acetic acid ethyl ester(0.380 g, 27%). 1H NMR (400 MHz, DMSO-d6δ 9.30 (s, 1H), 9.02 (s, 1H), 6.88 (s, 1H), 6.68 (s, 1H), 5.40 (m, 1H), 4.00 (m, 2H), 3.00 (m, 1H), 2.50 (m, 2H), 2.20 (m, 1H), 1.20 (m, 3H).

Workup

  1. temperatureAfter cooling down to 37° C.
  2. additionAfter addition
  3. temperatureto cool to room temperature over 30 minutes
  4. stirringThe mixture was stirred for 10 minutes
  5. extractionextracted with EtOAc (2×25 mL)
  6. washThe organic extracts were washed with brine
  7. dry with materialdried over anhydrous MgSO4
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by silica gel flash column chromatography

Sources & evidence

ORD record
ord-cedb8e023fb74e2995d962ab888fccb8
Source dataset
uspto-grants-2013_01
Patent number
US08343944B2

Reaction notes

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