1,4-Bis(diphenylphosphino)butane → 2-[3,4-Dichloro-5-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)phenyl]ethanol

HRID 337586

Reaktionsgleichung

Reaktionsgleichung von HRID 337586
[Cl:1][C:2]1[C:7]([Cl:8])=[CH:6][C:5]([CH:9]=[CH2:10])=[CH:4][C:3]=1[CH2:11][O:12][Si:13]([C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:15])[CH3:14].C1C=CC(P(C2C=CC=CC=2)CCCCP(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC1(C)C(C)(C)OB[O:52]1.B(O[O-])=O.[Na+]>C1COCC1>[Cl:8][C:7]1[CH:6]=[C:5]([CH2:9][CH2:10][OH:52])[CH:4]=[C:3]([CH2:11][O:12][Si:13]([C:16]([CH3:19])([CH3:18])[CH3:17])([CH3:14])[CH3:15])[C:2]=1[Cl:1]

Komponenten

6

Edukt 4

HCID 821241,4-Bis(diphenylphosphino)butaneHCID 517072Sodium PerborateHCID 27347684,4,5,5-Tetramethyl[1,3,2]dioxaborolaneHCID 66896286{[(2,3-Dichloro-5-ethenylphenyl)methyl]oxy}(1,1-dimethylethyl)dimethylsilane

Produkt 1

HCID 668954032-[3,4-Dichloro-5-({[(1,1-dimethylethyl)(dimethyl)silyl]oxy}methyl)phenyl]ethanol

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

{[(2,3-Dichloro-5-ethenylphenyl)methyl]oxy}(1,1-dimethylethyl)dimethylsilane (1 eq.) from the previous step, [Ir(COD)Cl]2 (0.025 eq.) and DPPB (0.05 eq.) were combined in THF (0.11 M). To this solution was then added 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.3 eq.) and the resulting red solution was stirred at RT for 16 h. Finally, sodium perborate (0.1 M aqueous solution, 1 eq.) was added and the now black biphasic solution was vigorously stirred at RT for another 8 h. The aqueous layer was separated and back-extracted with ether. The combined organic extracts were then washed further with 1 N aq. NaOH, water and brine. This was then dried over Na2SO4, filtered and the filtrate concentrated in vacuo to afford a black oil. Purification of the crude product thus obtained by way of flash chromatography (SiO2, 9:1 (v/v) Hex:EtOAc→1:1 (v/v) EtOAc:Hex) afforded the title compound as a pale yellow oil.

Aufarbeitung

  1. customThe aqueous layer was separated
  2. extractionback-extracted with ether
  3. washThe combined organic extracts were then washed further with 1 N aq. NaOH, water and brine
  4. dry with materialThis was then dried over Na2SO4
  5. filtrationfiltered
  6. concentrationthe filtrate concentrated in vacuo
  7. customto afford a black oil
  8. customPurification of the crude product
  9. customthus obtained by way of flash chromatography (SiO2, 9:1 (v/v) Hex:EtOAc→1:1 (v/v) EtOAc:Hex)

Quellen und Nachweise

ORD-Eintrag
ord-79ae79cb15c04ed587a2eab76c91597c
Quelldatensatz
uspto-grants-2014_11
Patentnummer
US08889714B2

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