Chlorotrimethylsilane → HCID 67252189, compound

HRID 1798067Notes

Reaction equation

HRID 1798067 reaction equation
C[Si](Cl)(C)C.Br[CH2:7][C:8]([O:10][CH2:11][CH3:12])=[O:9].[CH3:13][O:14][C:15]1[CH:22]=[C:21]([O:23][CH:24]2[CH2:29][CH2:28][CH2:27][CH2:26][O:25]2)[CH:20]=[C:19]([B:30]2[O:34][C:33](C)(C)C(C)(C)[O:31]2)[C:16]=1C=O>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]([O:23][CH:24]3[CH2:29][CH2:28][CH2:27][CH2:26][O:25]3)[CH:22]=[C:15]([O:14][CH3:13])[C:16]1=2)[CH3:12]

Participants

6

Reactant 3

HCID 6397ChlorotrimethylsilaneHCID 7748Ethyl bromoacetateHCID 86653975HCID 86653975, compound

Product 1

HCID 67252189HCID 67252189, compound

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
55 °C

Procedure

To a mixture of zinc powder (0.98 g, 15.0 mmol) in anhydrous THF (30 mL) was added TMSCl (0.39 mL, 3.0 mmol) at 40° C. The resulting mixture was stirred at 55° C. for 15 min and cooled to 37° C. After addition of ethyl 2-bromoacetate (1.35 mL, 12.0 mmol), the reaction mixture was stirred at this temperature for an additional 30 min. To a solution of 2-methoxy-4-(tetrahydro-2H-pyran-2-yloxy)-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzaldehyde (1.09 g, 3.0 mmol) in anhydrous THF (40 mL) was added dropwise the above prepared solution at −78° C. The reaction mixture was allowed to warm to room temperature and stirred for 1.5 h before quenched by aqueous ammonium chloride (20 mL). The resulting mixture was extracted with ethyl acetate (50 mL×2) and the combined organic layers were dried over anhydrous Na2SO4 and concentrated in vacuo. The residue was purified by column chromatography (EtOAc/PE=1/4) on silica gel to give the title compound as a yellow solid. (0.86 g, Y: 82.3%). MS (ESI) m/z=267 [M+H]+.

Workup

  1. temperaturecooled to 37° C
  2. stirringthe reaction mixture was stirred at this temperature for an additional 30 min
  3. temperatureto warm to room temperature
  4. stirringstirred for 1.5 h
  5. custombefore quenched by aqueous ammonium chloride (20 mL)
  6. extractionThe resulting mixture was extracted with ethyl acetate (50 mL×2)
  7. dry with materialthe combined organic layers were dried over anhydrous Na2SO4
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by column chromatography (EtOAc/PE=1/4) on silica gel

Sources & evidence

ORD record
ord-9cc6df4042d149ec9bbfe5f948ff43e1
Source dataset
uspto-grants-2013_01
Patent number
US08343944B2

Reaction notes

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