Triisopropyl borate → HCID 57898728, compound

HRID 1811759Notes

Reaction equation

HRID 1811759 reaction equation
[C:1]([Si:5]([O:8][C:9]1[CH:14]=[C:13](I)[C:12]([Cl:16])=[CH:11][C:10]=1[Cl:17])([CH3:7])[CH3:6])([CH3:4])([CH3:3])[CH3:2].C(=O)=O.CC(C)=O.[CH:25]([O:28][B:29](OC(C)C)[O:30][CH:31](C)C)(C)C.C([Li])[CH2:39][CH2:40][CH3:41]>O1CCCC1.C1(C)C=CC=CC=1>[Si:5]([O:8][C:9]1[C:10]([Cl:17])=[CH:11][C:12]([Cl:16])=[C:13]([B:29]2[O:30][CH2:31][C:40]([CH3:39])([CH3:41])[CH2:25][O:28]2)[CH:14]=1)([C:1]([CH3:4])([CH3:3])[CH3:2])([CH3:7])[CH3:6]

Participants

7

Reactant 4

HCID 21531Triisopropyl borateHCID 18522661Acetone cardiceHCID 57898847HCID 57898847, compoundHCID 178418339Butyllithium

Product 1

HCID 57898728HCID 57898728, compound

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8028TetrahydrofuranSolvent

Procedure

A solution of tert-butyl(2,4-dichloro-5-iodophenoxy)dimethylsilane (857 mg) obtained in Step 1 above in tetrahydrofuran (1 ml) and toluene (4 ml) was prepared under nitrogen atmosphere. The solution was cooled to −78° C. (dry ice/acetone). After triisopropylborate (0.6 ml) was added, n-butyllithium (1.6N; n-hexane solution, 1.62 ml) was added dropwise thereto over 5 minutes. The mixture was stirred at the same temperature for 30 minutes, and then warmed by removing the cold bath. When the inner temperature reached 0° C., 2,2-dimethylpropane-1,3-diol (0.27 g) was added to the solution and then warmed to room temperature. After stirring at room temperature for 8 hours, water (20 ml) was added to the solution and extracted with ethyl acetate (20 ml). The ethyl acetate solution was sequentially washed with a half-saturated aqueous ammonium chloride solution (15 ml), water (15 ml), and a saturated aqueous sodium chloride solution (10 ml). Then, the organic solution was pre-dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off. The resulting residue was purified by silica gel column chromatography (developing solvent: n-hexane:ethyl acetate=20:1 to 9:1) to yield pale yellow oily 2-[5-(tert-butyldimethylsilanyloxy)-2,4-dichlorophenyl]-5,5-dimethyl[1,3,2]dioxaborinane (547 mg).

Workup

  1. temperaturewarmed
  2. customby removing the cold bath
  3. customreached 0° C.
  4. addition2,2-dimethylpropane-1,3-diol (0.27 g) was added to the solution
  5. stirringAfter stirring at room temperature for 8 hours
  6. additionwater (20 ml) was added to the solution
  7. extractionextracted with ethyl acetate (20 ml)
  8. washThe ethyl acetate solution was sequentially washed with a half-saturated aqueous ammonium chloride solution (15 ml), water (15 ml)
  9. dry with materialThen, the organic solution was pre-dried over anhydrous sodium sulfate
  10. filtrationAfter filtration
  11. distillationthe solvent was distilled off
  12. customThe resulting residue was purified by silica gel column chromatography (developing solvent: n-hexane:ethyl acetate=20:1 to 9:1)

Sources & evidence

ORD record
ord-4f753a4173ff441eab7b791f2ac42b09
Source dataset
uspto-grants-2013_01
Patent number
US08362236B2

Reaction notes

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