Chlorotrimethylsilane → HCID 58292869, compound

HRID 1798263Notes

Reaction equation

HRID 1798263 reaction equation
C[Si](Cl)(C)C.[CH2:6]([O:13][C:14]1[CH:21]=[C:20]([O:22][CH:23]2[CH2:28][CH2:27][CH2:26][CH2:25][O:24]2)[CH:19]=[C:18]([B:29]2[O:33]C(C)(C)[C:31]([CH3:37])(C)[O:30]2)[C:15]=1C=O)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1>C1COCC1.[Zn]>[CH2:20]([O:22][C:23](=[O:24])[CH2:37][CH:31]1[O:30][B:29]([OH:33])[C:18]2[CH:19]=[C:20]([O:22][CH:23]3[CH2:28][CH2:27][CH2:26][CH2:25][O:24]3)[CH:21]=[C:14]([O:13][CH2:6][C:7]3[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=3)[C:15]1=2)[CH3:19]

Participants

5

Reactant 2

HCID 6397ChlorotrimethylsilaneHCID 58292674HCID 58292674, compound

Product 1

HCID 58292869HCID 58292869, compoundYield 145.4%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalystHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
55 °C

Procedure

A suspension of Zn (2.91 g, 44.5 mmol) in THF (10 mL) was added TMSCl (0.833 ml, 6.57 mmol) at 40° C. The temperature was increased to 55° C. over 30 min. Then, the temperature was lowered to 37° C. and bromo ethyl acetate (4.55 mL, 41.1 mmol) was added slowly. The resulting solution was stirred for 30 min from 45° C. to room temperature and stood by for 1 h. The top clear layer (3 mL) was added to a solution of 2-benzyloxy-4-(tetrahydro-pyran-2-yloxy)-6-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-benzaldehyde (1.50 g, 3.42 mmol) in THF (5 ml) at −78° C. After the addition, the reaction was warmed to 0° C. using an ice bath and stirred at 0° C. 30 min. The reaction mixture was quenched with NH4Cl and extracted with ethyl acetate. The organic phase was separated, dried (Na2SO4), and concentrated. The residue was purified by the flash column chromatography (silica, hexanes/ethyl acetate=3:2) to afford the title compound (1.06 g, 73%). MS calcd for (C23H27BO7+H)+: 427.2. MS found: (M+H)+=427.2.

Workup

  1. customwas lowered to 37° C.
  2. customstood by for 1 h
  3. additionAfter the addition
  4. temperaturethe reaction was warmed to 0° C.
  5. stirringstirred at 0° C
  6. custom30 min
  7. customThe reaction mixture was quenched with NH4Cl
  8. extractionextracted with ethyl acetate
  9. customThe organic phase was separated
  10. dry with materialdried (Na2SO4)
  11. concentrationconcentrated
  12. customThe residue was purified by the flash column chromatography (silica, hexanes/ethyl acetate=3:2)

Sources & evidence

ORD record
ord-a155c261b26c464f90ab6b22b5e99464
Source dataset
uspto-grants-2013_01
Patent number
US08343944B2

Reaction notes

Loading…